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

Abstract

The present application provides a resin composition, 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, the resin composition including a non-ionic base generator that generates a base having a pyridine structure by the action of light or heat, a precursor of a cyclized resin, and a photopolymerization initiator or a photoacid generator.

Description

Technical Field

[0001] This invention relates to a resin composition, a cured product, a laminate, a method for manufacturing the cured product, and a semiconductor device. Background Technology

[0002] Cyclic resins such as polyimide are suitable for a wide range of applications due to their excellent heat resistance and insulation properties. These applications are not particularly limited; for example, in the case of semiconductor devices used in actual installation, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can be used as base films and cover films for flexible substrates.

[0003] For example, in the above-described applications, cyclized resins such as polyimide are used in the form of resin compositions containing precursors of cyclized resins such as polyimide precursors.

[0004] For example, such resin compositions can be applied to a substrate to form a photosensitive film by coating, and then exposed, developed, heated, etc., as needed, thereby forming a cured product on the substrate.

[0005] The precursors of the aforementioned cyclized resins, such as polyimide precursors, are cyclized in the cured product by heating, thus becoming cyclized resins such as polyimide.

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability. For example, it offers a high degree of design freedom in terms of the shape, size, and application location of the resin composition. Considering both the high performance of cyclized resins such as polyimide and this excellent manufacturing adaptability, the expansion of industrial applications for the aforementioned resin composition is increasingly promising.

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

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2011-121962 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] In resin compositions used to obtain cured products, it is desirable that the resulting cured product exhibits excellent rectangularity of pattern.

[0013] The present invention aims to provide a resin composition that can produce a cured product with excellent pattern rectangularity, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate.

[0014] means for solving technical problems

[0015] The following are examples of representative embodiments of the present invention.

[0016] <1> A resin composition comprising:

[0017] Nonionic base-generating agents that produce bases with pyridine structures through the action of light or heat;

[0018] Precursors to cyclized resins; and

[0019] Photopolymerization initiator or photoacid generator.

[0020] <2> A resin composition comprising:

[0021] Base-generating agents containing amide groups with a dihydropyridine structure;

[0022] Precursors to cyclized resins; and

[0023] Photopolymerization initiator or photoacid generator.

[0024] <3> according to <2> The resin composition, wherein,

[0025] The above-mentioned alkali generating agent is a nonionic alkali generating agent.

[0026] <4> according to <1> to <3> The resin composition described in any one of the following statements, wherein,

[0027] The aforementioned alkali-generating agent is a compound represented by the following formula (1-1).

[0028] [Chemical Formula 1]

[0029]

[0030] In equation (1-1), L 1 R represents an n+m valence linkage group. 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them can bond together to form a ring structure, X independently represents a hydroxyl or a carboxyl group, n represents an integer of 1 or more, and m represents an integer of 1 or more.

[0031] <5> according to <1> to <4> The resin composition described in any one of the following statements, wherein,

[0032] The aforementioned alkali-generating agent is a compound represented by the following formula (1-2).

[0033] [Chemical Formula 2]

[0034]

[0035] In equation (1-2), L 2 and L 3 Each can be used independently to represent a single bond or a divalent linked group; Ar represents an aromatic group that can have substituents; R... 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them can bond together to form a ring structure, X independently represents a hydroxyl or a carboxyl group, x represents an integer greater than 1, and y represents an integer greater than 1.

[0036] <6> according to <1> to <5> The resin composition described in any one of the following statements comprises a photoradical polymerization initiator.

[0037] <7> according to <1> to <6> The resin composition described in any one of the following statements comprises a polymerizable compound.

[0038] <8> according to <1> to <7> The resin composition described in any one of the following is used to form an interlayer insulating film for a rewiring layer.

[0039] <9> A solidified substance, which is cured <1> to <8> It is made of the resin composition described in any one of the above.

[0040] <10> A laminate comprising two or more layers made of <9> The cured material forms layers in which metal layers are interposed between any of the layers formed by the cured material.

[0041] <11> A method for manufacturing a cured product, comprising applying a curing agent onto a substrate. <1> to <8> The film forming process of forming a film using the resin composition described in any one of the above statements.

[0042] <12> according to <11> The method for manufacturing the cured material includes an exposure step of selectively exposing the film and a development step of developing the film using a developing solution to form a pattern.

[0043] <13> according to <11> or <12> The method for manufacturing the cured material includes a heating step of heating the film at 50 to 450°C.

[0044] <14> A semiconductor device comprising <9> The solidified material or <10> The aforementioned laminated body.

[0045] Invention Effects

[0046] According to the present invention, a resin composition that can produce a cured product with excellent pattern rectangularity is provided, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate. Detailed Implementation

[0047] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0048] In this specification, the numerical range indicated by the symbol “~” refers to the range including the lower limit and upper limit values ​​recorded before and after “~”, respectively.

[0049] In this specification, the term "process" refers not only to independent processes, but also to processes that cannot be clearly distinguished from other processes, provided that the intended function of the process can be achieved.

[0050] In this specification, the designations of groups (atomic groups) include those without substituted and unsubstituted designations, encompassing both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0051] Unless otherwise specified, "exposure" in this manual includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Moreover, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation.

[0052] In this specification, "(meth)acrylate" means "acrylate" and "methacrylate" or either one; "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" or either one; and "(meth)acryloyl" means "acryloyl" and "methacryloyl" or either one.

[0053] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula.

[0054] In this specification, total solids content refers to the total mass of all components of the composition other than the solvent. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0055] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene conversion values. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. When THF is unsuitable as the eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, a UV (ultraviolet) detector with a wavelength of 254 nm is used for detection in GPC measurements.

[0056] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or third element may be further sandwiched between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. Moreover, unless otherwise specified, the direction of stacking relative to the substrate layers is referred to as "upper," or when a resin composition layer is present, the direction from the substrate towards the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, these vertical and horizontal directions are set for convenience in this specification, and in practice, the "upper" direction in this specification may differ from the vertical direction.

[0057] Unless otherwise specified, in this specification, each component included in the composition may contain two or more compounds equivalent to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds equivalent to that component.

[0058] Unless otherwise specified, the temperature in this manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0059] In this specification, the preferred combination of methods is a more preferred method.

[0060] (Resin Composition)

[0061] The resin composition according to the first aspect of the present invention comprises a nonionic base generating agent that generates a base having a pyridine structure by means of light or heat, a precursor of a cyclized resin, and a photopolymerization initiator or photoacid generating agent.

[0062] The resin composition involved in the second aspect of the present invention comprises an alkali generating agent having an amide group containing a dihydropyridine structure, a precursor of a cyclized resin, and a photopolymerization initiator or a photoacid generating agent.

[0063] Hereinafter, the resin composition according to the first aspect of the present invention and the resin composition according to the second aspect of the present invention will also be collectively referred to as "resin composition".

[0064] Furthermore, the base generating agent that produces a base having a pyridine structure by means of light or heat, which belongs to the first aspect of the present invention, and the base generating agent having an amide group containing a dihydropyridine structure, which belongs to the second aspect of the present invention, are described as "specific base generating agents".

[0065] The resin composition of the present invention is preferably used to form photosensitive films for exposure and development, and more preferably to form films for exposure and development using a developer containing an organic solvent.

[0066] The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for rewiring layers.

[0067] Furthermore, the resin composition of the present invention can be used to form a photosensitive film for positive development or a photosensitive film for negative development.

[0068] In this invention, during exposure and development, negative development refers to development that removes the non-exposed areas, while positive development refers to development that removes the exposed areas.

[0069] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and developing method described in the developing step can be used.

[0070] According to the resin composition of the present invention, a cured film with excellent rectangular pattern can be obtained.

[0071] The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0072] Resin compositions containing resins and alkali-generating agents have been used in various fields for a long time.

[0073] For example, by using a composition containing a precursor of a cyclized resin such as a polyimide precursor and an alkali generating agent, heating the composition or otherwise causes alkali to be generated from the alkali generating agent, thereby cyclizing the precursor of the cyclized resin and obtaining a cured product containing a cyclized resin such as a polyimide resin.

[0074] Here, the inventors have conducted research and found that when conventional alkali generating agents are used, the pattern rectangularity of the cured product is poor.

[0075] This is believed to be because the diffusion of alkali is hindered by the addition reaction between secondary alkalis and other alkalis generated from conventional alkali-generating agents and carbonyl groups, C=C groups, etc. in the resin. As a result, it is not easy for the resin to cyclize uniformly inside the layer formed by the composition.

[0076] In the resin compositions of the present invention, the base generating agents include nonionic base generating agents that generate bases having a pyridine structure by means of light or heat, or base generating agents having amide groups containing a dihydropyridine structure. The bases generated from such base generating agents have low reactivity with the aforementioned resins, and are therefore considered to diffuse easily within the composition film.

[0077] Therefore, it is believed that resin cyclization can easily proceed uniformly within the film, thereby improving the rectangularity of the pattern.

[0078] Furthermore, it is believed that the composition exhibits excellent storage stability because the structure of the alkali-generating agent used in this invention is close to neutral.

[0079] Furthermore, it is believed that as a result of the resin cyclization proceeding easily and uniformly as described above, the cyclization rate of the resin is also improved, and the elongation at break of the cured product is also excellent.

[0080] Furthermore, it is believed that because the C=C groups and other polymeric groups contained in resins, polymeric compounds, etc., can be reduced by reacting with the aforementioned alkali, the crosslinking density in the cured film can be easily increased, and the chemical resistance is also excellent.

[0081] Here, Patent Document 1 does not describe a specific alkali-generating agent.

[0082] The components contained in the resin composition of the present invention will be described in detail below.

[0083] <Specific Resin>

[0084] The resin composition of the present invention comprises a precursor of a cyclized resin (a specific resin).

[0085] Cyclic resins are preferably resins that contain an imide ring structure or an oxazole ring structure in their main chain structure.

[0086] In this invention, the main chain refers to the longest bonded chain in the resin molecule.

[0087] Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide.

[0088] The precursor of a cyclized resin refers to a resin whose chemical structure changes through external stimulation to become a cyclized resin. Preferably, it is a resin whose chemical structure changes through heat to become a cyclized resin, and more preferably, it is a resin that forms a ring structure through a ring-closing reaction caused by heat to become a cyclized resin.

[0089] Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

[0090] That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from polyimide precursor, polybenzoxazole precursor and polyamide-imide precursor as a specific resin.

[0091] The resin composition of the present invention preferably contains a polyimide precursor as a specific resin.

[0092] Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0093] When a particular resin has free radical polymerizable groups, the resin composition of the present invention preferably contains a free radical polymerization initiator (described later), more preferably contains both the free radical polymerization initiator (described later) and the free radical crosslinking agent (described later). A sensitizer (described later) may also be included if necessary. Thus, the resin composition of the present invention can, for example, form a negative photosensitive film.

[0094] Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups.

[0095] When a particular resin has acid-degrading groups, the resin composition of the present invention preferably contains the photoacid-generating agent described later. Thus, the resin compositions of the present invention can, for example, form chemically amplified positive or negative photosensitive films.

[0096] [Polyimide precursor]

[0097] The polyimide precursor used in this invention is not particularly limited to any particular type, but preferably contains repeating units represented by the following formula (2).

[0098] [Chemical Formula 3]

[0099]

[0100] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115R represents a tetravalent organic group. 113 and R 114 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0101] A in equation (2) 1 and A 2 Each can be represented independently as an oxygen atom or -NH-, with oxygen atom being preferred.

[0102] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups comprising aromatic groups with 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the cyclic hydrocarbon groups in the aforementioned cyclic aliphatic and aromatic groups can be replaced by groups containing heteroatoms. As a preferred embodiment of the present invention, R is exemplified. 111 Examples of groups represented by -Ar- and -Ar-L-Ar- are provided, with groups represented by -Ar-L-Ar- being particularly preferred. Here, Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. The preferred ranges are as described above.

[0103] R 111 The preferred diamine is derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0104] Specifically, the preferred diamine is a diamine comprising a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof; more preferably, a diamine comprising an aromatic group having 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the cyclic hydrocarbon groups of the aforementioned cyclic aliphatic and aromatic groups can be replaced by groups containing heteroatoms. Examples of groups containing aromatic groups include the following groups.

[0105] [Chemical Formula 4]

[0106]

[0107] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0108] In the formula, * indicates the bonding site with other structures.

[0109] As a diamine, specifically, examples include at least one diamine selected from the following: 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl) ... Hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(2-aminophenoxy)phenyl] sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane 3,3'-Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-Diaminofluorene, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5- Diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, [4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl The following compounds are listed: 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'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0110] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0111] Furthermore, diamines having two or more alkylene glycol units on the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, may be preferred.

[0112] From the perspective of the flexibility of the obtained organic membrane, R 111 Preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0113] Moreover, from the perspective of i-ray transmittance, R 111 Preferably, it is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0114] Equation (51)

[0115] [Chemical Formula 5]

[0116]

[0117] In equation (51), R 50 ~R 57 Each can be independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * represents the bonding site with the nitrogen atom in formula (2) independently.

[0118] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0119] [Chemical Formula 6]

[0120]

[0121] In equation (61), R 58 and R 59 Each of the above can be independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2).

[0122] Examples of diamines that impart the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used.

[0123] R in equation (2) 115 This indicates a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.

[0124] In equation (5) or equation (6), * independently represents the bonding site with other structures.

[0125] [Chemical Formula 7]

[0126]

[0127] In equation (5), R 112 It is a single bond or a divalent linker, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof, more preferably a single bond, a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0128] Specifically, R 115 Examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. As equivalent to R... 115 The structure of the polyimide precursor can contain only one type of tetracarboxylic acid dianhydride residue or more than two types.

[0129] Tetracarboxylic acid dianhydride is preferably represented by the following formula (0).

[0130] [Chemical Formula 8]

[0131]

[0132] In equation (0), R 115 R represents a tetravalent organic group. 115 R in equation (2) 115 They have the same meaning and the same preferred range.

[0133] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives thereof having 1 to 6 carbon atoms.

[0134] Furthermore, as a preferred example, one could cite tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0135] In equation (2), R 111 and R 115 At least one of them can also have an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0136] R in equation (2) 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferred to include straight-chain or branched alkyl groups, cyclic alkyl groups, aromatic groups, or polyalkoxide groups. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. The polymerizable group is a group capable of cross-linking reactions by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having olefinic unsaturated bonds is preferred.

[0137] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, etc.

[0138] [Chemical Formula 9]

[0139]

[0140] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0141] In equation (III), * indicates the bonding site with other structures.

[0142] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0143] R 201 Preferred examples include alkylene compounds such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkoxide compounds; more preferably, alkylene compounds such as vinyl and propenyl, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds; and even more preferably, alkylene compounds such as vinyl and propenyl or polyalkoxide compounds.

[0144] In this invention, polyalkoxide refers to a group formed by the direct bonding of two or more alkoxide groups. The alkylene groups in the multiple alkoxide groups contained in the polyalkoxide group may be the same or different.

[0145] When a polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0146] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0147] Furthermore, the aforementioned alkylene groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0148] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repeats of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0149] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethoxy, or groups formed by the bonding of multiple ethyleneoxy groups and multiple propyleneoxy groups are preferred as polyvinyloxy or polypropyleneoxy groups, and polyvinyloxy groups are even more preferred. In the aforementioned groups formed by the bonding of multiple ethyleneoxy and multiple propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, form blocks, or be arranged in alternating patterns. The preferred manner for the repetition of the ethyleneoxy groups, etc., in these groups is as described above.

[0150] In equation (2), in R 113 For the case of hydrogen atoms or R 114 In the case of hydrogen atoms, polyimide precursors can form conjugated salts with tertiary amine compounds having olefinically unsaturated bonds. N,N-dimethylaminopropyl methacrylate is an example of such tertiary amine compounds having olefinically unsaturated bonds.

[0151] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it is decomposed by the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups. It is preferred to use acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. From the point of view of exposure sensitivity, acetal groups or ketal groups are more preferred.

[0152] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0153] Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0154] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0155] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in this invention is preferably 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, the range of exposure latitude can be further increased.

[0156] Equation (2-A)

[0157] [Chemical Formula 10]

[0158]

[0159] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, preferably both of them are groups containing polymerizable groups.

[0160] A 1 A 2 R 111 R 113 and R 114 Independently with A in equation (2) 1 A 2 R 111 R 113 and R 114 They have the same meaning and the same preferred range.

[0161] R 112 R in equation (5) 112 They have the same meaning and the same preferred range.

[0162] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units. Moreover, it may contain structural isomers of the repeating unit represented by formula (2). Furthermore, in addition to the repeating unit of formula (2) above, the polyimide precursor may obviously also contain other types of repeating units.

[0163] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the end units can be repeating units represented by formula (2).

[0164] 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 even more preferably 15,000 to 40,000. Furthermore, the number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0165] The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0166] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0167] Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are each within the aforementioned ranges.

[0168] [Polybenzoxazole precursor]

[0169] The structure of the polybenzoxazole precursor used in this invention is not particularly limited, but it preferably contains repeating units represented by the following formula (3).

[0170] [Chemical Formula 11]

[0171]

[0172] In equation (3), R121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0173] In equation (3), R 123 and R 124 respectively with R in equation (2) 113 The meanings are the same, and the preferred ranges are also the same. That is, at least one of them is preferably a polymeric group.

[0174] In equation (3), R 121 This indicates a divalent organic group. Preferably, the divalent organic group comprises at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. R 121 The preferred choice is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

[0175] As dicarboxylic acid residues, dicarboxylic acid residues containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred.

[0176] As a dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and a dicarboxylic acid composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The straight-chain aliphatic group is preferably an alkylene group.

[0177] Examples of dicarboxylic acids containing straight-chain aliphatic groups 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, and 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid Acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

[0178] [Chemical Formula 12]

[0179]

[0180] (In the formula, Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0181] As a dicarboxylic acid containing aromatic groups, a dicarboxylic acid having the following aromatic groups is preferred, and a dicarboxylic acid consisting only of a group having the following aromatic groups and two -COOH groups is more preferred.

[0182] [Chemical Formula 13]

[0183]

[0184] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * represents the bonding site with other structures independently.

[0185] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and terephthalic acid.

[0186] In equation (3), R 122 This represents a tetravalent organic group. As a tetravalent organic group, it is related to R in the above formula (2). 115 They have the same meaning and the same preferred range.

[0187] Moreover, R 122Preferably, the group is derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-( 4-Amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These diaminophenols can be used alone or in combination.

[0188] Among the diaminophenol derivatives, those having the following aromatic groups are preferred.

[0189] [Chemical Formula 14]

[0190]

[0191] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. Furthermore, R... 122 The structure represented by the above formula is also preferred. R 122 When the structure is represented by the above formula, among the four * and #, it is preferable that any two are R in formula (3). 122 The bonding sites of the nitrogen atoms are the same as those of the other two atoms, which are related to R in equation (3). 122 The bonding sites of the bonded oxygen atoms are preferably two associating with R in equation (3). 122 The bonding sites of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the nitrogen atoms or the two asterisks are related to R in equation (3). 122 The bonding sites of the nitrogen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the bonded oxygen atoms are further preferably two as R in equation (3). 122The bonding sites of the bonded oxygen atoms and the two #'s are related to R in equation (3). 122 The bonding sites of the nitrogen atoms.

[0192] The diaminophenol derivative is preferably a compound represented by formula (As).

[0193] [Chemical Formula 15]

[0194]

[0195] In formula (As), R1 is an organic group selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or the following formulas (A-sc). R2 is any one of hydrogen atom, alkyl, alkoxy, acyloxy, or cyclic alkyl, and may be the same or different. R3 is any one of hydrogen atom, straight-chain or branched alkyl, alkoxy, acyloxy, or cyclic alkyl, and may be the same or different.

[0196] [Chemical Formula 16]

[0197]

[0198] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0199] It is considered that having a substituent at the ortho position of the phenolic hydroxyl group, i.e., at R3, in the above formula (As) would bring the carbonyl carbon of the amide bond closer to the hydroxyl group, and would further improve the effect of increasing the cyclization rate when cured at low temperature.

[0200] Furthermore, in the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, it is possible to maintain high transparency to i-rays and high cyclization rate during low-temperature curing, which is therefore preferred.

[0201] Furthermore, in the above formula (As), R1 is preferably an alkylene or substituted alkylene. Specific examples of the alkylene and substituted alkylene involved in R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred, considering the ability to obtain a polybenzoxazole precursor with sufficient solubility in solvents and excellent balance while maintaining high transparency to i-rays and high cyclization rate during low-temperature curing.

[0202] As for the method of manufacturing the diaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, which are incorporated herein by reference.

[0203] Specific examples of the structures of bisaminophenol derivatives represented by the above formula (As) can be found in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, which are incorporated herein by reference. However, this is not the only possible explanation.

[0204] In addition to the repeating unit in formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units.

[0205] From the viewpoint of being able to suppress the warping that accompanies the ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0206] [Chemical Formula 17]

[0207]

[0208] In equation (SL), Z has structures a and b, and R 1s R is a hydrocarbon group consisting of 1 to 10 hydrogen atoms or carbon atoms. 2s R is a hydrocarbon group with 1 to 10 carbon atoms. 3s R 4s R 5s R 6s At least one of the components is an aromatic group, and the remaining components are organic groups consisting of hydrogen atoms or 1 to 30 carbon atoms, which may be the same or different. The polymerization of structures a and b can be block polymerization or random polymerization. Regarding the molar percentage of the Z portion, structure a is 5–95 mol%, structure b is 95–5 mol%, and a+b is 100 mol%.

[0209] In equation (SL), Z, as a preferred option, can be represented by R in structure b. 5s and R 6s Examples include phenyl groups. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, while simultaneously achieving the effects of suppressing warpage and improving solvent solubility.

[0210] When a diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. An example of such a tetracarboxylic acid residue is R in formula (2). 115 Examples.

[0211] For example, the weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0212] The molecular weight dispersion of the aforementioned polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular upper limit to the molecular weight dispersion of the polybenzoxazole precursor; for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and still even more preferably 2.2 or less.

[0213] Furthermore, when the resin composition contains multiple polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polybenzoxazole precursors as a single resin are each within the aforementioned ranges.

[0214] [Polyamide-imide precursor]

[0215] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2).

[0216] [Chemical Formula 18]

[0217]

[0218] In formula (PAI-2), R 117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, R 113 It represents a hydrogen atom or a monovalent organic group.

[0219] In formula (PAI-2), R 117Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these groups together by single bonds or linking groups. Preferably, straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups together by single bonds or linking groups. More preferably, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms together by single bonds or linking groups.

[0220] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are more preferred.

[0221] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0222] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, with all hydrogen atoms preferably being replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0223] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0224] Moreover, R 117 Preferably, the compound is a tricarboxylic acid compound derived from at least one carboxyl group that can be halogenated. Chlorination is preferred as the halogenation method.

[0225] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0226] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-substituted.

[0227] Examples of halogenable tricarboxylic acid compounds used to manufacture polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0228] These tricarboxylic acid compounds can be used in one or more forms.

[0229] Specifically, as a tricarboxylic acid compound, it is preferable to be a tricarboxylic acid compound comprising a straight-chain 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 tricarboxylic acid compound comprising two or more of these groups by means of single bonds or linking groups. More preferably, it is a tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a tricarboxylic acid compound comprising two or more of the aromatic groups having 6 to 20 carbon atoms by means of single bonds or linking groups.

[0230] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid linked by single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or phenylene oxide, etc.

[0231] These compounds can be compounds formed by anhydride conversion of two carboxyl groups (e.g., trimellitic anhydride) or compounds formed by halogenation of at least one carboxyl group (e.g., trimellitic anhydride chloride).

[0232] In formula (PAI-2), R 111 A 2 R 113 respectively with R in the above formula (2) 111 A 2 R 113 The meanings are the same, and the preferred selection methods are also the same.

[0233] The polyamide-imide precursor may also contain other repeating units.

[0234] Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).

[0235] [Chemical Formula 19]

[0236]

[0237] In formula (PAI-1), R 116 R represents a divalent organic group. 111 It represents a divalent organic group.

[0238] In formula (PAI-1), R 116Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these groups together by single bonds or linking groups. Preferably, straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups together by single bonds or linking groups. More preferably, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms together by single bonds or linking groups.

[0239] As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are preferred, and -O-, -S-, alkylene, alkylene halide, arylene, or linking groups formed by bonding two or more of these are more preferred.

[0240] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0241] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, with all hydrogen atoms preferably being replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0242] As the aforementioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

[0243] Moreover, R 116 Preferably, the compounds are derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0244] In this invention, compounds having two carboxyl groups are referred to as dicarboxylic acid compounds, and compounds having two halogenated carboxyl groups are referred to as dicarboxylic acid dihalides.

[0245] The carboxyl group in a dicarboxylic acid dihalide compound can be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

[0246] Examples of halogenable dicarboxylic acid compounds or dicarboxylic acid dihalides used to manufacture polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0247] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in one or more forms.

[0248] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferable to be a dicarboxylic acid compound or a dicarboxylic acid dihalide compound that comprises a straight-chain 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 groups through single bonds or linking groups. More preferably, it is a dicarboxylic acid compound or a dicarboxylic acid dihalide compound that comprises 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 through single bonds or linking groups.

[0249] Furthermore, specific examples of dicarboxylic acid compounds 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, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, and hexafluoro... Sebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyldiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0250] As a specific example of a dicarboxylic acid dihalide compound, a compound with a structure in which two carboxyl groups of the above-mentioned dicarboxylic acid compound examples are halogenated can be cited.

[0251] In formula (PAI-1), R 111 R in equation (2) above 111The meanings are the same, and the preferred selection methods are also the same.

[0252] Furthermore, the polyamide-imide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0253] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., as the diamine component.

[0254] As one embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamide-imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).

[0255] Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited; all repeating units in the polyamide-imide precursor, except for the terminal units, can be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0256] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0257] The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0258] Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide-imide precursor are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyamide-imide precursors as a single resin are each within the aforementioned ranges.

[0259] [Methods for manufacturing polyimide precursors, etc.]

[0260] For example, polyimide precursors can be obtained by methods such as: reacting tetracarboxylic dianhydride with diamine at low temperature; reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid and esterifying it with a condensing agent or alkylating agent; obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting it in the presence of diamine and a condensing agent; obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine. Of the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferred. Of the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferred.

[0261] Examples of condensing agents include dicyclohexanediimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0262] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0263] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0264] In methods for manufacturing polyimide precursors, organic solvents are preferably used during the reaction. One or more organic solvents may be used.

[0265] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0266] In methods for manufacturing polyimide precursors, a basic compound is preferably added during the reaction. The basic compound can be one type or two or more types.

[0267] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0268] -End- Capping Agent-

[0269] When manufacturing polyimide precursors, etc., to further improve storage stability, it is preferable to end-cap the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of the polyimide precursor, etc. When end-capping the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monools, phenols, thiols, benzenethiophenols, monoamines, etc. Considering reactivity and film stability, monools, phenols, and monoamines are more preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0270] Furthermore, when blocking the amino groups at the resin ends, compounds having functional groups that can react with the amino groups can be used for blocking. Preferred end-blocking agents for the amino groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Preferred compounds for carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentanoyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0271] -Solid precipitation-

[0272] The manufacture of polyimide precursors may include a solid precipitation process. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain the polyimide precursor. To improve the purification degree, the polyimide precursor may be repeatedly subjected to operations such as re-dissolving, re-precipitating, and drying. A further step may be included to remove ionic impurities using an ion exchange resin.

[0273] 〔content〕

[0274] The content of a specific resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and still even more preferably 95% by mass or less.

[0275] The resin composition of the present invention may contain only one specific resin or may contain two or more resins. When containing two or more resins, the total amount is preferably within the above-mentioned range.

[0276] Furthermore, the resin composition of the present invention preferably contains at least two resins.

[0277] Specifically, the resin composition of the present invention may contain two or more specific resins and other resins described below, or may contain two or more specific resins, preferably two or more specific resins.

[0278] When the resin composition of the present invention contains two or more specific resins, it is preferable, for example, to contain a structure derived from dianhydride (R in formula (2) above). 115 Two or more different polyimide precursors.

[0279] <Other Resins>

[0280] The resin composition of the present invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0281] Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins.

[0282] For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can also be obtained.

[0283] For example, by replacing the polymerizable compound described later in the resin composition or by adding a polymerizable group with a weight average molecular weight of less than 20,000 and a high polymerizable group value (e.g., the molar content of polymerizable groups in 1g of resin is 1×10⁻⁶) in addition to the polymerizable compound described later in the resin composition. -3 (Meth)acrylic resins with a molar ratio of 100 mol / g or higher can improve the coatability of resin compositions, the solvent resistance of patterns (cured products), etc.

[0284] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0285] Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0286] Furthermore, as a preferred embodiment of the resin composition of the present invention, it is also possible to configure it with a low content of other resins. In the above embodiment, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, and 0% by mass or more is acceptable.

[0287] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, the total amount is preferably within the above-mentioned range.

[0288] <Specific Alkali Generators>

[0289] The resin composition according to the first aspect of the present invention contains a nonionic base generating agent that produces a base having a pyridine structure by means of light or heat.

[0290] The nonionic nature of the aforementioned nonionic base generator refers to the fact that it is a compound represented by a single molecule rather than in the form of an association formed by the proximity of an organic molecule with an anionic structure and an organic molecule with a cationic structure.

[0291] The aforementioned nonionic base generating agent is preferably a nonionic base generating agent that generates a base having a pyridine structure by means of heat. It is more preferably generated by heating to 250°C, more preferably by heating to 220°C, even more preferably by heating to 200°C, particularly preferably by heating to 190°C, and most preferably by heating to 180°C. The lower limit of the temperature for base generation is not particularly limited, but from the viewpoint of the storage stability of the composition, for example, 100°C or higher is preferred.

[0292] Furthermore, when the aforementioned nonionic base generating agent is a nonionic base generating agent that generates a base having a pyridine structure by means of light, it is preferable to generate the base by means of light with a wavelength of 190 nm to 450 nm, more preferably by means of light with a wavelength of 250 nm to 450 nm, even more preferably by means of light with a wavelength of 350 nm to 420 nm, and especially preferably by means of i-rays or h-rays.

[0293] The following method can be used to determine whether a nonionic base generator exhibits the property of producing a base with a pyridine structure at a temperature of X °C.

[0294] In a sealed container, at 1 atmosphere and X °C, 1 mole of a nonionic base-generating agent is heated for 3 hours. The amount of decomposition is then quantified using methods such as HPLC (High-Speed ​​Liquid Chromatography). The generation of 0.01 moles or more of a pyridine-structured base is defined as "generating a pyridine-structured base." Whether the generated base is a pyridine-structured base is determined, for example, by using... 1 The amount of the base having the pyridine structure produced is preferably 0.1 moles or more, more preferably 0.5 moles or more. There is no particular upper limit to the amount of the base having the pyridine structure produced; for example, it can be set to 1000 moles or less.

[0295] The following method can be used to determine whether a nonionic base generator exhibits the property of producing a base with a pyridine structure by the action of some kind of light.

[0296] Composition A, obtained by dissolving a nonionic alkali-generating agent in a solvent, was prepared under conditions of 1 atmosphere pressure and 25°C, with an exposure illuminance of 25 W / cm². 2 Under certain conditions, after irradiation with light of wavelength 190–800 nm for 30 seconds, the amount of decomposition is quantitatively determined by methods such as HPLC (high-speed liquid chromatography). The condition where a base with a pyridine structure is produced at least 0.01 mol% relative to the total molar amount of the nonionic base-generating agent is defined as "producing a base with a pyridine structure". When the resin composition contains a solvent, the concentration of the nonionic base-generating agent in composition A can be set to the same as the concentration in the resin composition, and the type of solvent in the composition can be set to the same as the solvent contained in the resin composition. Furthermore, when the resin composition does not contain a solvent, the concentration of the nonionic base-generating agent in composition A relative to the total mass of composition A can be set to approximately 1.0% by mass, and the solvent can be N-methyl-2-pyrrolidone, etc.

[0297] The amount of the base having the pyridine structure produced is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. There is no particular upper limit to the amount of the base having the pyridine structure produced; for example, it can be set to 1000 mol% or less.

[0298] The bases with the pyridine structure mentioned above can be, for example, pyridine, pyridine with substituents, or heterocyclic structures (e.g., fused ring structures) containing the pyridine structure.

[0299] Furthermore, the molecular weight of the base having the pyridine structure is preferably 79 to 1,000, more preferably 80 to 500, and even more preferably 100 to 400.

[0300] The boiling point of the above-mentioned pyridine-based base at 1 atmosphere is preferably 50-600°C, more preferably 60-500°C, and even more preferably 80-450°C.

[0301] There are no particular limitations on specific examples of bases having a pyridine structure; bases with the following structures can be cited as examples.

[0302] [Chemical Formula 20]

[0303]

[0304] The nonionic base generating agent involved in the first aspect of the present invention preferably has an amide group containing a dihydropyridine structure.

[0305] The alkali generating agent involved in the second aspect of the present invention has an amide group containing a dihydropyridine structure.

[0306] The alkali generating agent involved in the second aspect of the present invention is preferably a nonionic alkali generating agent.

[0307] The alkali-generating agent involved in the second aspect of the present invention preferably generates an alkali having a pyridine structure by means of light or heat. The method for confirming the generation of an alkali having a pyridine structure by means of light or heat, and the preferred methods for temperature or light wavelength, are as described above.

[0308] The above-mentioned dihydropyridine structure can be a dihydropyridine structure with substituents, or a heterocyclic structure containing a dihydropyridine structure (e.g., a fused ring structure).

[0309] The amide group containing the dihydropyridine structure is preferably represented by the following formula (DH-1).

[0310] [Chemical Formula 21]

[0311]

[0312] The dihydropyridine structure in formula (DH-1) can have substituents or form heterocyclic structures with other ring structures. * indicates the bonding site with other structures.

[0313] The preferred base generating agent is a compound represented by formula (1-1).

[0314] [Chemical Formula 22]

[0315]

[0316] In equation (1-1), L 1 R represents an n+m valence linkage group. 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them can bond together to form a ring structure, X independently represents a hydroxyl or a carboxyl group, n represents an integer of 1 or more, and m represents an integer of 1 or more.

[0317] In equation (1-1), L 1 Preferably, it consists of a hydrocarbon group or a combination of one or more hydrocarbon groups and a group selected from heterocyclic groups, -O-, -C(=O)-, -S-, -S(=O2)-, and -NR. N - A group represented by a combination of at least one structure in -, more preferably a hydrocarbon group or a group composed of one or more hydrocarbon groups and selected from -O-, -S- and -NR-. N - A group representing a combination of at least one structure in -. As the above-mentioned heterocyclic group, a heteroaromatic cyclic group is preferred. Furthermore, examples of heteroatoms included in the heterocyclic group include oxygen atoms, sulfur atoms, nitrogen atoms, etc. The above-mentioned R N It represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0318] The aforementioned hydrocarbon group can be any one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, preferably containing at least an aromatic hydrocarbon group, and more preferably a group represented by a combination of an aromatic hydrocarbon group and an aliphatic hydrocarbon group.

[0319] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 20 carbon atoms is preferred, and a group having multiple hydrogen atoms removed from the benzene ring is more preferred. Furthermore, the aforementioned aromatic hydrocarbon group may have substituents or may form a fused ring with other ring structures.

[0320] As the aforementioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferred, a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms is more preferred, a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms is even more preferred, and a saturated aliphatic hydrocarbon group with 1 to 4 carbon atoms is particularly preferred.

[0321] Furthermore, when X is a hydroxyl group, L 1 The number of atoms (linkage length) in the path of the linking chain between X and -C(=O)- is preferably 3 to 6, more preferably 3 or 4.

[0322] When X is a carboxyl group, the number of atoms (linkage chain length) in the path of the linking chain between X and -C(=O)- is preferably 2 to 5, more preferably 2 or 3.

[0323] L 1 It may have polymerizable groups, and preferably has free radical polymerizable groups.

[0324] Moreover, L 1 When the precursor of the cyclized resin has a free radical polymerizable group, it is preferable that the precursor of the cyclized resin has a free radical polymerizable group or that the resin composition contains at least one of the free radical crosslinking agents described later.

[0325] According to this approach, since the polymer formed by polymerization contains an alkali-generating agent, the distribution of the alkali-generating agent in the composition is nearly uniform, thus further improving the rectangularity of the pattern.

[0326] As L 1 Specific examples, such as the structures described below, are given, but are not limited to. In the following specific examples, * represents the bonding site with X in equation (1-1), and # represents the bonding site with -C(=O)- in equation (1-1).

[0327] [Chemical Formula 23]

[0328]

[0329] In equation (1-1), R 2 ~R 6 Each of these groups independently represents a hydrogen atom, a halogen atom, or a monovalent organic group, more preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxyalkyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. These groups may further have substituents such as a nitro group.

[0330] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl or ethyl.

[0331] The aryl group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group.

[0332] The alkoxy group of the above-mentioned alkoxyalkyl group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methoxy or ethoxy group.

[0333] The number of carbon atoms from the bonding site to the oxygen atom in the above-mentioned alkoxyalkyl group is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0334] The alkyl group in the above-mentioned alkoxycarbonyl group is preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and even more preferably methyl or ethyl.

[0335] The aryl group in the above-mentioned aryloxycarbonyl group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group.

[0336] In formula (1-1), X independently represents a hydroxyl group or a carboxyl group, with a hydroxyl group being preferred.

[0337] In formula (1-1), n ​​is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0338] In formula (1-1), m is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0339] Furthermore, the specific base generating agent is preferably a compound represented by the following formula (1-2).

[0340] [Chemical Formula 24]

[0341]

[0342] In equation (1-2), L 2 and L 3 Each can be used independently to represent a single bond or a divalent linked group; Ar represents an aromatic group that can have substituents; R... 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them can bond together to form a ring structure, X independently represents a hydroxyl or a carboxyl group, x represents an integer greater than 1, and y represents an integer greater than 1.

[0343] In formula (1-2), X is preferably a hydroxyl group.

[0344] In equation (1-2), L 2 Preferably, it is a single bond, a hydrocarbon group, or a combination of one or more hydrocarbon groups and a group selected from -O-, -C(=O)-, -S-, -S(=O2)-, and -NR. N - The group represented by a combination of at least one structure in - is more preferably a single bond or a hydrocarbon group, and even more preferably a single bond or an alkylene group.

[0345] As the aforementioned hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms is preferred, and a hydrocarbon group having 1 to 4 carbon atoms is more preferred.

[0346] As the aforementioned alkylene group, alkylene groups having 1 to 10 carbon atoms are preferred, and alkylene groups having 1 to 4 carbon atoms are more preferred.

[0347] In formula (1-2), Ar is preferably an aromatic hydrocarbon group that may have at least one of a substituent and a fused ring, and more preferably a group that removes multiple hydrogen atoms from a benzene ring structure that may have at least one of a substituent and a fused ring.

[0348] Examples of substituents in Ar include nitro, vinyl, and ester groups.

[0349] Examples of aromatic hydrocarbon groups with fused rings include benzofuran rings, benzothiophene rings, and indole rings, but they are not limited to these.

[0350] In equation (1-2), L 3 Preferably, it is a single bond or selected from hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O2)-, and -NR. N- at least one group, or a group represented by a combination thereof, more preferably at least one group selected from hydrocarbon groups, -O- and -C(=O)-, or a group represented by a combination thereof. R N As described above.

[0351] In equation (1-2), R 2 ~R 6 These represent hydrogen atoms, halogen atoms, or monovalent organic groups, respectively, preferably hydrogen atoms or monovalent organic groups.

[0352] As the aforementioned monovalent organic group, alkyl, aryl, alkoxyalkyl, alkoxycarbonyl, or aryloxycarbonyl are more preferred. These groups may further have substituents such as nitro.

[0353] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl or ethyl.

[0354] The aryl group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group.

[0355] The alkoxy group of the above-mentioned alkoxyalkyl group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methoxy or ethoxy group.

[0356] The number of carbon atoms from the bonding site to the oxygen atom in the above-mentioned alkoxyalkyl group is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0357] The alkyl group in the above-mentioned alkoxycarbonyl group is preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and even more preferably methyl or ethyl.

[0358] The aryl group in the above-mentioned aryloxycarbonyl group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group.

[0359] In formula (1-2), x is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0360] In formula (1-2), y is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0361] [Molecular weight]

[0362] The molecular weight of the specific alkali generating agent is preferably 150 to 1,000, more preferably 180 to 800, and even more preferably 200 to 700.

[0363] [Synthesis Method]

[0364] Certain base-generating agents can be synthesized, for example, by the condensation reaction of dihydropyridine compounds with carboxylic acid compounds or by the addition reaction of dihydropyridine compounds to carboxylic acid halides. Furthermore, they can also be synthesized using other known synthetic methods, and there are no particular limitations on the synthetic methods used.

[0365] There are no particular limitations on specific examples of base generating agents, but examples A-1 to A-35 used in the examples can be cited.

[0366] The content of the specific alkali-generating agent is preferably 0.5 to 20% by mass relative to the total solids content of the resin composition of the present invention. The lower limit is more preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0367] A specific alkali generating agent can be used alone or in combination with two or more. When using two or more, the total dosage is preferably within the range mentioned above.

[0368] Furthermore, when the resin composition of the present invention comprises a specific alkali generating agent and a alkali generating agent (different from the specific alkali generating agent) described later, the total content of the specific alkali generating agent and the alkali generating agent (different from the specific alkali generating agent) is preferably 0.5 to 20% by mass. The lower limit is more preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0369] The content of the specific alkali generating agent relative to the total mass of the specific resin is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and even more preferably 1 to 20% by mass.

[0370] Organometallic complexes

[0371] From the viewpoint of drug resistance, the resin composition of the present invention may contain organometallic complexes.

[0372] Organometallic complexes are any organic complex compounds containing metal atoms, preferably complex compounds containing metal atoms and organic groups, more preferably compounds in which organic groups are coordinated with metal atoms, and even more preferably metallocene compounds.

[0373] In this invention, metallocene compounds refer to organometallic complexes containing two cyclopentadienyl anionic derivatives that may have substituents as η5-ligands.

[0374] The organic group mentioned above is not particularly limited, but a hydrocarbon group or a group composed of a hydrocarbon group and a heteroatom is preferred. As for the heteroatom, oxygen atom, sulfur atom, and nitrogen atom are preferred.

[0375] In this invention, it is preferred that at least one of the organic groups is a cyclic group, and more preferably at least two of them are cyclic groups.

[0376] The aforementioned cyclic group is preferably selected from 5-membered ring cyclic groups and 6-membered ring cyclic groups, and more preferably from 5-membered ring cyclic groups.

[0377] The aforementioned cyclic group can be a hydrocarbon ring or a heterocycle, with a hydrocarbon ring being preferred.

[0378] As a cyclic group of a 5-membered ring, cyclopentadienyl is preferred.

[0379] Furthermore, the organometallic complexes used in this invention preferably contain 2 to 4 cyclic groups per molecule.

[0380] The metal included in the organometallic complex is not particularly limited, but it is preferred to be a metal belonging to Group 4 elements, more preferably at least one metal selected from titanium, zirconium and hafnium, even more preferably at least one metal selected from titanium and zirconium, and especially preferably titanium.

[0381] Organometallic complexes can contain two or more metal atoms, or they can contain only one metal atom, preferably only one metal atom. When organometallic complexes contain two or more metal atoms, they can contain only one type of metal atom or two or more types of metal atoms.

[0382] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconium diacene compound, or a hafnium diacene compound, more preferably a titanocene compound, a zirconium diacene compound, or a hafnium diacene compound, even more preferably a titanocene compound or a zirconium diacene compound, and especially preferably a titanocene compound.

[0383] The ability of organometallic complexes to initiate photoradical polymerization is also one of the preferred methods of this invention.

[0384] In this invention, the ability to initiate photoradical polymerization refers to the ability to generate free radicals capable of initiating free radical polymerization through light irradiation. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light but the free radical crosslinking agent does not, the presence or absence of photoradical polymerization initiation ability can be confirmed by checking whether the free radical crosslinking agent disappears. When confirming whether it has disappeared, an appropriate method can be selected according to the type of free radical crosslinking agent, such as IR measurement (infrared spectroscopy) or HPLC measurement (high-performance liquid chromatography).

[0385] 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 zirconium diacene compound, or a hafnium diacene compound, even more preferably a titanocene compound or a zirconium diacene compound, and especially preferably a titanocene compound.

[0386] When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is preferably selected from at least one compound selected from titanium diacene compounds, tetraalkoxy titanium compounds, acylated titanium compounds, chelated titanium compounds, zirconium diacene compounds, and hafnium diacene compounds; more preferably selected from at least one compound selected from titanium diacene compounds, zirconium diacene compounds, and hafnium diacene compounds; even more preferably selected from at least one compound selected from titanium diacene compounds and zirconium diacene compounds; and especially preferably titanium diacene compounds.

[0387] The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

[0388] As organometallic complexes, compounds represented by the following formula (P) are preferred examples.

[0389] [Chemical Formula 25]

[0390]

[0391] In formula (P), M is a metal atom, and R are independent substituents.

[0392] The R mentioned above is preferably selected independently from aromatic groups, alkyl groups, halogen atoms and alkylsulfonyloxy groups.

[0393] In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, even more preferably a titanium atom or a zirconium atom, and especially preferably a titanium atom.

[0394] As an aromatic group in R in formula (P), examples include aromatic groups with 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups with 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl.

[0395] As for the alkyl group in formula (P), it is preferably an alkyl group with 1 to 20 carbon atoms, and more preferably an alkyl group with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc.

[0396] Examples of halogen atoms in R include F, Cl, Br, and I.

[0397] As the alkyl group constituting the alkyl sulfonyloxy group in the above-mentioned R, it is preferably an alkyl group with 1 to 20 carbon atoms, and more preferably an alkyl group with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc.

[0398] The R group mentioned above can further have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0399] Specific examples of organometallic complexes are not particularly limited, and examples include tetraisopropoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetoacetate) titanium, diisopropoxybis(acetylacetone) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium, pentamethylcyclopentadientrimethoxy titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium, and the following compounds.

[0400] [Chemical Formula 26]

[0401]

[0402] In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 may be used, but are not limited thereto.

[0403] The content of the organometallic complex relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.

[0404] One or more organometallic complexes can be used. When two or more are used, the total amount is preferably within the range mentioned above.

[0405] <Polymerizing compounds>

[0406] The resin composition of the present invention preferably contains a polymerizable compound.

[0407] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0408] [Free radical cross-linking agent]

[0409] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0410] A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferably, the free radical polymerizable group contains an olefinically unsaturated bond. Examples of such olefinically unsaturated groups include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido groups.

[0411] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred groups containing olefinic unsaturated bonds, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0412] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may have three or more olefinic unsaturated bonds.

[0413] As for the above-mentioned compounds having two or more olefinic unsaturated bonds, compounds having 2 to 15 olefinic unsaturated bonds are preferred, compounds having 2 to 10 olefinic unsaturated bonds are more preferred, and compounds having 2 to 6 olefinic unsaturated bonds are even more preferred.

[0414] Furthermore, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains compounds having two olefinic unsaturated bonds and compounds having three or more of the above-mentioned olefinic unsaturated bonds.

[0415] The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

[0416] Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyols, and amides of unsaturated carboxylic acids and polyamines. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Moreover, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are even more preferred. Furthermore, as other examples, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can be used. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0417] Furthermore, the free radical crosslinking agent is preferably a compound with a boiling point of 100°C or higher at normal pressure. Examples 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, glycerol, or trimethylolethane, which are added to polyfunctional alcohols with ethylene oxide or propylene oxide followed by (meth)acrylate addition. Esterified compounds, urethane (meth)acrylates described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as products of the reaction of epoxy resin and (meth)acrylic acid, and other polyfunctional acrylates or methacrylates; and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are preferred. Moreover, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having cyclic ether groups and olefinic unsaturated bonds, such as glycidyl (meth)acrylate, can also be cited.

[0418] Furthermore, as a preferred free radical crosslinking agent other than those mentioned above, compounds having a fluorene ring and having two or more groups having olefinic unsaturated bonds, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, as well as cardo resins, can also be used.

[0419] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, etc., can also be used. Moreover, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, compounds introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0420] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 are also preferred to be used, and these contents are incorporated in this specification.

[0421] Furthermore, the compounds described in Japanese Patent Application Publication No. 10-062986 as formulas (1) and (2) along with their specific examples can also be used as free radical crosslinking agents. These compounds are obtained by esterification of (meth)acrylates after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0422] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and this information is incorporated into this specification.

[0423] As free radical crosslinking agents, preferred options include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku Co., Ltd.)), A-TMMT (Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (Nippon Kayaku Co., Ltd.)), A-DPH (Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0424] Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four vinyl groups) and SR-209, 231, and 239 (difunctional methacrylates with four vinyl groups) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentylene groups) and TPA-330 (a trifunctional acrylate with three isobutyryl groups) manufactured by Nippon Kayaku Co., Ltd.; urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUS TRIES 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.); and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). (manufactured by Kyoisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

[0425] As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and urethane compounds having an ethylene oxide backbone described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418 are also preferred. Furthermore, compounds having an amino or thioether structure within the molecule as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 can also be used as free radical crosslinking agents.

[0426] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent having acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol in the free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

[0427] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1–300 mg KOH / g, particularly preferably 1–100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and, consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid values ​​were measured according to the description in JIS K 0070:1992.

[0428] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylates or acrylates.

[0429] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, etc. Dimethacrylates, including dimethylol-tricyclodecane dimethacrylates, dimethylol-tricyclodecane dimethacrylates, ethylene oxide (EO) adduct dimethacrylates of bisphenol A, EO adduct dimethacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylates, EO-modified dimethacrylates of isocyanuric acid, isocyanuric acid-modified dimethacrylates, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0430] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0431] From the viewpoint of suppressing warping caused by controlling the elastic modulus of the accompanying pattern (cured product), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferred materials include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and allyl glycidyl ether. As a monofunctional free radical crosslinking agent, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred to suppress volatilization before exposure.

[0432] In addition, examples of allyl compounds, such as diallyl phthalate and triallyl trimellitate, can be cited as free radical crosslinking agents with two or more functions.

[0433] When a free radical crosslinking agent is included, its content relative to the total solids content of the resin composition of the present invention is preferably more than 0% by mass and less than 60% by mass. 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.

[0434] Free radical crosslinking agents can be used alone or in combination of two or more. When using two or more, their combined dosage is preferably within the range mentioned above.

[0435] [Other crosslinking agents]

[0436] The resin composition of the present invention preferably also contains other crosslinking agents different from the free radical crosslinking agents described above.

[0437] In this invention, other crosslinking agents refer to crosslinking agents other than the aforementioned free radical crosslinking agents. Preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds and their reaction products in the composition by photosensitization by the aforementioned photoacid generator or photobase generator. More preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds and their reaction products in the composition by the action of an acid or base.

[0438] The acid or base mentioned above is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure process.

[0439] As other crosslinking agents, compounds having at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from acyloxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0440] Other crosslinking agents include, for example, compounds having the following structure: obtained by reacting amino-containing compounds such as melamine, acetylacetonate, urea, alkylene urea, and benzoguanidine with formaldehyde or formaldehyde and an alcohol, thereby replacing the hydrogen atoms of the aforementioned amino groups with acyloxymethyl, hydroxymethyl, or alkoxymethyl groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, these compounds can be oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds.

[0441] As for the aforementioned amino-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using acetylenide, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanidine are called benzoguanidine-based crosslinking agents.

[0442] The resin composition of the present invention preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from acetylene urea-based crosslinking agents and melamine-based crosslinking agents described later.

[0443] As a compound containing at least one of alkoxymethyl and acylmethyl groups in this invention, examples of compounds in which the alkoxymethyl or acylmethyl group is directly substituted on an aromatic group, a nitrogen atom of a urea structure described below, or a triazine are provided.

[0444] Regarding the alkoxymethyl or acylmethyl groups present in the above-mentioned compounds, it is preferred that the number of carbon atoms is 2 to 5, more preferably 2 or 3, and even more preferably 2.

[0445] The total number of alkoxymethyl and acylmethyl groups in the above-mentioned compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0446] The molecular weight of the above-mentioned compound is preferably below 1500, and more preferably between 180 and 1200.

[0447] [Chemical Formula 27]

[0448]

[0449] R 100 Indicates alkyl or acyl groups.

[0450] R 101 and R 102 Each of these groups independently represents a monovalent organic group and can bond with each other to form a ring.

[0451] Compounds in which alkoxymethyl or acylmethyl groups are directly substituted on aromatic groups include, for example, compounds of the following general formula.

[0452] [Chemical Formula 28]

[0453]

[0454] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each can be independently represented by an alkyl or acyl group, R 103 This refers to a group consisting of a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to form a base-soluble group (e.g., a group that is released by the action of an acid, or a group formed by -C(R)). 4 )2COOR 5 The group represented (R) 4 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 5 This indicates a group that is released by the action of an acid.

[0455] R 105 Each can independently represent an alkyl or alkenyl group, where a, b, and c are each 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.

[0456] Regarding groups that decompose under the action of acid to form alkali-soluble groups, groups that are released under the action of acid, and groups derived from -C(R) 4 )2COOR 5 The R in the indicated group 5 For example, one can cite -C(R) 36 (R) 37 (R) 38 ), -C(R 36 (R) 37 (OR) 39 ), -C(R 01 (R) 02 (OR) 39 )wait.

[0457] In the formula, R 36 ~R 39 Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R 36 With R 37 They can bond together to form a ring.

[0458] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0459] The aforementioned alkyl groups can be either straight-chain or branched.

[0460] As the aforementioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred.

[0461] The aforementioned cycloalkyl groups can be monocyclic or polycyclic structures such as fused rings.

[0462] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and more preferably a phenyl group.

[0463] As the aforementioned aralkyl group, aralkyl groups with 7 to 20 carbon atoms are preferred, and alkyl groups with 7 to 16 carbon atoms are more preferred.

[0464] The aryl group mentioned above refers to an aryl group that has been substituted with an alkyl group. The preferred methods for these alkyl and aryl groups are the same as those for the alkyl and aryl groups mentioned above.

[0465] The alkenyl group mentioned above is preferably an alkenyl group with 3 to 20 carbon atoms, and more preferably an alkenyl group with 3 to 16 carbon atoms.

[0466] Moreover, these groups can further have known substituents within the scope of achieving the effects of the present invention.

[0467] R 01 and R 02 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

[0468] The preferred groups, such as tertiary alkyl esters, acetals, cumyl esters, and enols, are those that decompose under acidic action to form alkali-soluble groups or are released under acidic action. Tertiary alkyl esters and acetals are more preferred.

[0469] As compounds having an alkoxymethyl group, specific examples include the following structures. Compounds having an acylmethyl group include those in which the alkoxymethyl group of the following compounds is replaced with an acylmethyl group. As compounds having an alkoxymethyl group or an acylmethyl group intramolecularly, the following compounds can be cited, but are not limited to these.

[0470] [Chemical Formula 29]

[0471]

[0472] [Chemical Formula 30]

[0473]

[0474] Compounds containing at least one of alkoxymethyl and acylmethyl groups can be commercially available or synthesized by known methods.

[0475] From the viewpoint of heat resistance, compounds in which alkoxymethyl or acylmethyl groups are directly substituted on the aromatic ring or triazine ring are preferred.

[0476] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0477] Specific examples of urea-based crosslinking agents include monohydroxymethylated acetylenoid, dihydroxymethylated acetylenoid, trihydroxymethylated acetylenoid, tetrahydroxymethylated acetylenoid, monomethoxymethylated acetylenoid, dimethoxymethylated acetylenoid, trimethoxymethylated acetylenoid, tetramethoxymethylated acetylenoid, monoethoxymethylated acetylenoid, diethoxymethylated acetylenoid, triethoxymethylated acetylenoid, tetraethoxymethylated acetylenoid, monopropoxymethylated acetylenoid, dipropoxymethylated acetylenoid, tripropoxymethylated acetylenoid, tetrapropoxymethylated acetylenoid, monobutoxymethylated acetylenoid, dibutoxymethylated acetylenoid, tributoxymethylated acetylenoid, or tetrabutoxymethylated acetylenoid, etc.

[0478] Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea.

[0479] Monohydroxymethylated vinylurea or dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea or dibutoxymethylated vinylurea, etc., are vinylurea-based crosslinking agents.

[0480] Acrylurea crosslinking agents such as monohydroxymethylated acrylate, dihydroxymethylated acrylate, monomethoxymethylated acrylate, dimethoxymethylated acrylate, monoethoxymethylated acrylate, diethoxymethylated acrylate, monopropoxymethylated acrylate, dipropoxymethylated acrylate, monobutoxymethylated acrylate, or dibutoxymethylated acrylate.

[0481] 1,3-Di(methoxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc.

[0482] Specific examples of benzoguanidine-based crosslinking agents include, for instance, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0483] Furthermore, as a compound having at least one group selected from hydroxymethyl and alkoxymethyl, it is also preferable to use a compound having at least one group selected from hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring).

[0484] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenylbenzene. Methyl ketone, methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4”-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0485] Other crosslinking agents can be commercially available products. Preferred commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, same below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALACMW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEM[CAL CO.,LTD), etc.

[0486] Furthermore, the resin composition of the present invention preferably contains at least one compound selected from epoxy compounds, oxetane compounds and benzoxazine compounds as other crosslinking agents.

[0487] -Epoxy compounds (compounds containing epoxy groups)-

[0488] As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy groups undergo cross-linking reactions below 200°C and do not trigger dehydration reactions due to cross-linking, thus minimizing film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition of the present invention can be effectively suppressed.

[0489] The epoxy compound preferably contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to a group in which ethylene oxide has two or more repeating units, preferably 2 to 15.

[0490] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones containing epoxy groups such as polymethyl(epoxypropoxypropyl)siloxane, but these are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-83OLVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, and EPICLON (registered trademark) N-740 (these are product names, DIC). (Manufactured by Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKACORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel). The following compounds are manufactured by Nippon Kayaku Co., Ltd.: 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 (trade names, manufactured by Nippon Kayaku Co., Ltd.). Furthermore, the following compounds are also preferred.

[0491] [Chemical Formula 31]

[0492]

[0493] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0494] In the above structure, considering both heat resistance and improved elongation, n is preferably 1 to 2 and m is preferably 3 to 7.

[0495] -Oxycyclic butane compounds (compounds containing an oxycyclic butyl group)-

[0496] Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetane-butyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetane-butyl)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. is preferred; these can be used alone or in mixtures of two or more.

[0497] -Benzoxazine compounds (compounds containing a benzoxazole group)-

[0498] Benzooxazine compounds are preferred because they do not undergo degassing during curing due to the crosslinking reaction caused by the ring-opening addition reaction, thereby reducing thermal shrinkage and inhibiting warping.

[0499] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and dihydrobenzoxazine compounds of phenolic varnish type. These can be used alone or in combination of two or more.

[0500] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. Other crosslinking agents may be present in only one type or in two or more types. When two or more other thermal crosslinking agents are present, their total content is preferably within the above-mentioned range.

[0501] [Polymerization initiator]

[0502] The resin compositions of the present invention preferably contain a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, photopolymerization initiators are preferred.

[0503] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator; it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, it can be an active agent that interacts with the photoexcited sensitizer and generates active free radicals.

[0504] The photoradical polymerization initiator preferably contains at least one initiator having a wavelength of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be measured using known methods. For example, it is preferred to use a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0505] As photoradical polymerization initiators, any known compounds can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azido compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0506] As ketone compounds, examples include those described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, KAYACUREDETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferred.

[0507] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, as these contents are incorporated herein by reference.

[0508] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACLRE is a registered trademark), DAROCUR1173, IRGACURE 500, IRGACURE-2959, and IRGACURE127 (trade names: all manufactured by BASF) can be used.

[0509] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0510] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which match the maximum absorption wavelength to a light source of wavelengths such as 365 nm or 405 nm, can also be used, and these contents are incorporated in this specification.

[0511] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Furthermore, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.

[0512] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.).

[0513] Oxime compounds are more preferably selected as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be further improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude and also act as photocuring accelerators.

[0514] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... The compounds described in Technology (1995, pp. 202-232), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0515] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy(imino))but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one. In the resin compositions of the present invention, oxime compounds (oxime-based photoradical polymerization initiators) are preferably used, particularly as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have an intramolecular linking group >C=NOC(=O)-.

[0516] [Chemical Formula 32]

[0517]

[0518] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052) are also preferred. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Additionally, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. Moreover, oxime compounds with the following structures can also be used.

[0519] [Chemical Formula 33]

[0520]

[0521] Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, which are incorporated herein by reference.

[0522] As photoradical polymerization initiators, oxime compounds with at least one benzene ring having a carbazole ring as the backbone of a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0523] Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, which are incorporated herein by reference.

[0524] Nitro-containing oxime compounds can be used as photopolymerization initiators. Nitro-containing oxime compounds are preferably dimers. Specific examples of nitro-containing oxime compounds include compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is another example of a nitro-containing oxime compound.

[0525] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0526] As photoradical polymerization initiators, oxime compounds with hydroxyl substituents bonded to the carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, which are incorporated herein by reference.

[0527] As a photopolymerization initiator, it is also possible to use aromatic cyclic groups Ar obtained by introducing electron-withdrawing groups into the aromatic ring. OX1 Oxime compounds (hereinafter also referred to as oxime compounds OX). As the above aromatic cyclic group Ar... OX1Examples of electron-withdrawing groups include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano, with acyl and nitro being preferred. Acyl is more preferred for the ease of forming a film with excellent lightfastness, and benzoyl is even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthioalkyl, arylthioalkyl, acyl, or amino, with alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthioalkyl, or amino being more preferred, and alkoxy, alkylthioalkyl, or amino being even more preferred.

[0528] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compounds represented by formula (OX2).

[0529] [Chemical Formula 34]

[0530]

[0531] In the formula, R X1 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphonyl, carbamoyl, or aminosulfonyl.

[0532] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0533] R X3 ~R X14 Each can be used to represent a hydrogen atom or a substituent independently.

[0534] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0535] In the above formula, R is preferred. X12 R is an electron-withdrawing group. X10 R X11 R X13 R X14 It is a hydrogen atom.

[0536] Specific examples of oxime compounds OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated herein by reference.

[0537] Examples of preferred oxime compounds include those with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061, which are incorporated herein by reference.

[0538] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0539] More preferably, the photoradical polymerization initiator is a trihalomethane triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, it is a compound selected from at least one of the following: trihalomethane triazine compound, α-amino ketone compound, metallocene compound, oxime compound, triarylimidazolium dimer, or benzophenone compound. Even more preferably, it is a metallocene compound or an oxime compound.

[0540] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by cyclization of aromatic rings with alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoin; and benzyl derivatives such as benzyl dimethyl ketal. Moreover, compounds represented by the following formula (I) can also be used.

[0541] [Chemical Formula 35]

[0542]

[0543] In equation (I), R I00The alkyl group having 1 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, the alkoxy group having 1 to 12 carbon atoms, the phenyl group, or the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the halogen atom, the cyclopentyl group, the cyclohexyl group, the alkenyl group having 2 to 12 carbon atoms, the alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and the alkyl group having 1 to 4 carbon atoms, are substituted with at least one phenyl or biphenyl group. I01 For groups represented by formula (II) or with R I00 The same group, R I02 ~R I04 Each is independently an alkyl group, an alkoxy group, or a halogen atom, having 1 to 12 carbon atoms.

[0544] [Chemical Formula 36]

[0545]

[0546] In the formula, R I05 ~R I07 R in equation (I) above I02 ~R I04 same.

[0547] Furthermore, the photoradical polymerization initiator can also use compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, which are incorporated in this specification.

[0548] As photoradical polymerization initiators, photoradical polymerization initiators with two or more functionalities can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Moreover, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents increases, making them less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. (G) Cmpd1 to 7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669 are included in this specification.

[0549] When a photopolymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may be only one type or may contain two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0550] In addition, photopolymerization initiators can sometimes also act as thermal polymerization initiators. Therefore, heating with ovens, heating plates, etc., can sometimes further promote crosslinking based on photopolymerization initiators.

[0551] [Sensitizer]

[0552] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases.

[0553] As usable sensitizers, compounds such as benzophenone, mifepristone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0554] Examples of sensitizers include mifepristone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylenepropyl dihydroindone, and p-dimethylaminophenylenepropyl dihydroindone. Aminophenylmethylene dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0555] Furthermore, other sensitizing pigments can also be used.

[0556] For details regarding the sensitizing pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0557] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used in combination.

[0558] [Chain transfer agent]

[0559] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferred.

[0560] Furthermore, the chain transfer agent can also use compounds described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0561] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, their total amount is preferably within the above-mentioned range.

[0562] [Photoacid generator]

[0563] The resin composition of the present invention preferably contains a photoacid generator.

[0564] A photoacid generator is a compound that generates at least one of Brønsted acid and Lewis acid by irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator capable of generating acid by photosensitivity is preferred.

[0565] Examples of acids that can be produced include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0566] Examples of photoacid generating agents used in the resin compositions of the present invention include, for example, quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfones, onium salts, etc.

[0567] From the perspective of sensitivity and storage stability, organic halogen compounds, oxime sulfonates, and onium salts are preferred. From the perspective of the mechanical properties of the formed membrane, oxime esters are preferred.

[0568] Examples of quinone diazide compounds include those formed by ester bonding of quinone diazide sulfonic acid with a mono- or poly-hydroxy compound, those formed by sulfonamide bonding of quinone diazide sulfonic acid with a mono- or poly-amino compound, and those formed by ester bonding and / or sulfonamide bonding of quinone diazide sulfonic acid with a polyhydroxy or polyamino compound. These polyhydroxy, polyamino, and polyhydroxy polyamino compounds do not require all functional groups to be replaced by quinone diazide; preferably, the average substituted functional groups are substituted by quinone diazide or more. By containing such quinone diazide compounds, resin compositions sensitive to ordinary ultraviolet light, i.e., i.e., mercury lamp i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm), can be obtained.

[0569] Specifically, examples of hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, 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, and Methylene. Tris-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, Honshu Chemical Industry The products include, but are not limited to, BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), phenolic varnish resins, etc.

[0570] As amino compounds, examples include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylene diamine, 1,3-phenylene diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, etc., but are not limited to these.

[0571] Moreover, examples of polyhydroxy polyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but these are not limited to.

[0572] Among them, the quinone diazide compound preferably includes a phenolic compound and an ester with a 4-naphthoquinone diazidesulfonyl group. This allows for higher sensitivity and higher resolution to i-ray exposure.

[0573] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by weight relative to 100 parts by weight of the resin, and more preferably 10 to 40 parts by weight. By setting the content of the quinone diazide compound within this range, a contrast between the exposed and unexposed portions can be obtained, thereby achieving high sensitivity, which is therefore preferred. Sensitizers, etc., may be further added as needed.

[0574] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compound").

[0575] There are no particular limitations on the presence of an oxime sulfonate group in the oxime sulfonate compound, but oxime sulfonate compounds represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) are preferred.

[0576] [Chemical Formula 37]

[0577]

[0578] In equation (OS-1), X 3 Indicates an alkyl, alkoxy, or halogen atom. X 3 When multiple instances exist, they can be the same or different. The aforementioned X... 3 The alkyl and alkoxy groups in X may have substituents. As described above, X... 3 The alkyl group in the text is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. As described above, X... 3 The alkoxy group in the above-mentioned X is preferably a straight-chain or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in the sample is preferably a chlorine atom or a fluorine atom.

[0579] In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or 1. When m3 is 2 or 3, multiple X 3 They can be the same or different.

[0580] In equation (OS-1), R 34The group represents an alkyl or aryl group, preferably an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 5 carbon atoms, a haloalkoxy group with 1 to 5 carbon atoms, a phenyl group that can be substituted with W, a naphthyl group that can be substituted with W, or an o-aminobenzoic acid group that can be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 5 carbon atoms, or a haloalkoxy group with 1 to 5 carbon atoms, an aryl group with 6 to 20 carbon atoms, or a haloaryl group with 6 to 20 carbon atoms.

[0581] In equation (OS-1), m3 is 3, X 3 Methyl, X 3 The replacement position is adjacent, R 34 Compounds that are straight-chain alkyl groups having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorborneolmethyl, or p-tolyl are particularly preferred.

[0582] Specific examples of oxime sulfonate compounds represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674, which are incorporated herein by reference.

[0583] [Chemical Formula 38]

[0584]

[0585] In equations (OS-103) to (OS-105), R s1 Some Rs represent alkyl, aryl, or heteroaryl groups, when multiple groups are present. s2 Some Rs, which independently represent hydrogen atoms, alkyl groups, aryl groups, or halogen atoms, when multiple Rs are present, s6 Each of these groups independently represents a halogen atom, alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group, or alkoxysulfonyl group. Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6.

[0586] In equations (OS-103) to (OS-105), R s1 The alkyl (preferably with 1 to 30 carbon atoms), aryl (preferably with 6 to 30 carbon atoms), or heteroaryl (preferably with 4 to 30 carbon atoms) indicated may have known substituents within the range of achieving the effects of the present invention.

[0587] In equations (OS-103) to (OS-105), R s2 The atom is preferably hydrogen, alkyl (preferably 1 to 12 carbon atoms) or aryl (preferably 6 to 30 carbon atoms), with hydrogen or alkyl being more preferred. s2When two or more atoms are present in the compound, it is preferable that one or two of them are alkyl, aryl, or halogen atoms; more preferably, one of them is an alkyl, aryl, or halogen atom; and particularly preferably, one of them is an alkyl atom and the rest are hydrogen atoms. (From R) s2 The alkyl or aryl groups represented may have known substituents within the range of achieving the effects of the present invention.

[0588] In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, preferably O. In formulas (OS-103) to (OS-105) above, the ring included by Xs as a cyclic atom is a 5-membered ring or a 6-membered ring.

[0589] In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is 0, ns is preferably 1, and when Xs is S, ns is preferably 2.

[0590] In equations (OS-103) to (OS-105), R s6 The alkyl group (preferably with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) may have substituents.

[0591] In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and especially preferably 0.

[0592] Furthermore, compounds represented by the above formula (OS-103) are particularly preferred to be compounds represented by the following formulas (OS-106), (OS-110), or (OS-111), especially preferred to be compounds represented by the above formula (OS-104), compounds represented by the following formula (OS-107), and especially preferred to be compounds represented by the above formula (OS-105), compounds represented by the following formula (OS-108) or (OS-109).

[0593] [Chemical Formula 39]

[0594]

[0595] In formula (OS-106) to formula (OS-111), R t1 R indicates alkyl, aryl, or heteroaryl. t7 R represents a hydrogen atom or a bromine atom. t8 Represents hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, halogen atoms, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl, R t9 R represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group. t2 It represents a hydrogen atom or a methyl group.

[0596] In formula (OS-106) to formula (OS-111), R t7 It represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

[0597] In formula (OS-106) to formula (OS-111), R t8 The atom represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and especially preferably a methyl group.

[0598] In formula (OS-106) to formula (OS-111), R t9 It represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, preferably a hydrogen atom.

[0599] R t2 It represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0600] Furthermore, the stereostructure (E, Z) of the oxime can be any of the aforementioned oxime sulfonate compounds, or a mixture thereof.

[0601] Specific examples of oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0602] As another preferred form of oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formulas (OS-101) and (OS-102) are examples.

[0603] [Chemical Formula 40]

[0604]

[0605] In formula (OS-101) or formula (OS-102), R u9 This indicates a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acyl, carbamoyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. More preferably, R. u9 In the form of cyano or aryl, R is further preferred. u9 It can be in the form of cyano, phenyl, or naphthyl.

[0606] In formula (OS-101) or formula (OS-102), R u2a Indicates alkyl or aryl.

[0607] In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR. u5 -, -CH2-, -CR u6 H- or CR u6 R u7 -, R u5 ~R u7 Each can be represented independently as either alkyl or aryl.

[0608] In formula (OS-101) or formula (OS-102), R u1 ~R u4 Each of these can independently represent a hydrogen atom, halogen atom, alkyl, alkenyl, alkoxy, amino, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, amide, sulfonyl, cyano, or aryl group. R u1 ~R u4 The two atoms in the ring can bond to each other to form a ring. At this point, the ring can condense and form a fused ring together with the benzene ring. As R... u1 ~R u4 Preferably, hydrogen atoms, halogen atoms, or alkyl groups are used, and R is also preferred. u1 ~R u4 The aryl group is formed by at least two of the molecules bonding with each other. Preferably, R... u1 ~R u4 All of these are hydrogen atoms. All of the above substituents can be further substituented.

[0609] The compound represented by the above formula (OS-101) is more preferably the compound represented by formula (OS-102).

[0610] Furthermore, the stereostructure of the oxime or benzothiazole ring (E, Z, etc.) can be any one of the above-mentioned oxime sulfonate compounds, or a mixture thereof.

[0611] Specific examples of compounds represented by formula (OS-101) include compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674, which are incorporated herein by reference.

[0612] Of the above compounds, b-9, b-16, b-31, and b-33 are preferred.

[0613] [Chemical Formula 41]

[0614]

[0615] Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0616] Furthermore, as a preferred example, compounds represented by the following structural formulas can also be cited.

[0617] [Chemical Formula 42]

[0618]

[0619] As organohalogenated compounds, examples include Wakabayashi et al., "Bull Chem. Soc Japan" 42,2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and MP Hutt's "Jurnal of Heterocyclic". Compounds described in Chemistry 1 (No. 3), (1970), etc., are incorporated herein by reference. In particular, as preferred examples, trihalomethyl-substituted oxazole compounds, such as triazine compounds, are cited.

[0620] More preferably, it is a triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is bonded to a triazine ring. Specifically, examples include 2,4,6-tris(monochloromethyl)-triazine, 2,4,6-tris(dichloromethyl)-triazine, 2,4,6-tris(trichloromethyl)-triazine, 2-methyl-4,6-bis(trichloromethyl)-triazine, 2-n-butyl-4,6-bis(trichloromethyl)-triazine, and 2... -(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-triazine, 2-phenyl-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-triazine, 2-[1-(p-methoxyphenyl) [2-(p-Butadienyl)-4,6-bis(trichloromethyl)-triazine, 2-styryl-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-naphthyloxy) Examples of trichloromethyl triazine include 2-phenylthio-4,6-bis(trichloromethyl)-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-triazine, 2,4,6-tris(dibromomethyl)-triazine, 2,4,6-tris(tribromomethyl)-triazine, 2-methyl-4,6-bis(tribromomethyl)-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-triazine.

[0621] As specific examples of organoborate compounds, Japanese Patent Application Publication Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837, 2002-107916, Japanese Patent No. 2764769, and 2002-116539, as well as Kunz, Martin, “Rad Tech’98. Proceeding April”, etc. Organoborates described in publications such as "Chicago" (19-22, 1998), organoboron sulfonium complexes or organoboron oxysulfonium complexes described in Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and organoboron iodine complexes described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553. The contents of this specification include complexes, organoboron-phosphorus complexes disclosed in Japanese Patent Application Publication No. 9-188710, organoboron-migrating metal coordination complexes disclosed in Japanese Patent Application Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014.

[0622] Examples of disulfone compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application Publication No. 2001-132318, as well as diazonium disulfone compounds.

[0623] Examples of the aforementioned onium salt compounds include, for instance, diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Balet al., Polymer, 21, 423 (1980); ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Publication No. 4-365049, etc.; phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056; European Patent Nos. 104,143, 339,049, and 410,201; iodine salts described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514; and European Patent Nos. 370,693 and 39... The matte salts described in the specifications of U.S. Patent No. 0,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, and JVCrivello, are... The selenium salts described in JVCrivello et al., Macromolecules, 10(6), 1307(1977), Polymer Sci., Polymer Chem. Ed., 17, 1047(1979), and the arsenic salts, pyridinium salts, and other onium salts described in CSWen et al., Teh, ProC. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) are included in this specification.

[0624] Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III).

[0625] [Chemical Formula 43]

[0626]

[0627] In formula (RI-I), Ar 11The term refers to an aryl group having 1 to 6 substituents and having 20 or fewer carbon atoms. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 2 to 12 carbon atoms, alkylamide groups having 1 to 12 carbon atoms in alkyl groups, or arylamide groups having 6 to 20 carbon atoms in aryl groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. 11 - The terms represent monovalent anions, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. Considering stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferred. In formula (RI-II), Ar... 21 Ar 22 Each of the substituents can independently represent an aryl group having 1 to 6 substituents and a carbon number of 1 to 20. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups with alkyl groups having 1 to 12 carbon atoms each, alkylamide groups or arylamide groups with alkyl groups having 1 to 12 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. 21 - The term represents a monovalent anion, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. Considering stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R... 31 R 32 R 33Each can independently represent an aryl or alkyl, alkenyl, or alkynyl group having 1 to 6 substituents and 6 to 20 carbon atoms. Aryl groups are preferred in terms of reactivity and stability. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms in each alkyl group, alkylamide or arylamide groups with 1 to 12 carbon atoms in each alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. 31 - The term represents monovalent anions, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. Considering stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred.

[0628] Specific examples of preferred photoacid generators include the following.

[0629] [Chemical Formula 44]

[0630]

[0631] [Chemical Formula 45]

[0632]

[0633] [Chemical Formula 46]

[0634]

[0635] [Chemical Formula 47]

[0636]

[0637] The photoacid generator is preferably used at 0.1 to 20% by mass relative to the total solids content of the resin composition, more preferably at 0.5 to 18% by mass, even more preferably at 0.5 to 10% by mass, even more preferably at 0.5 to 3% by mass, and even more preferably at 0.5 to 1.2% by mass.

[0638] A photoacid generator can be used alone or in combination. When multiple generators are used in combination, their total dosage is preferably within the range mentioned above.

[0639] Furthermore, in order to impart photosensitivity to the desired light source, it is preferable to use it in combination with a sensitizer.

[0640] <Alkali-generating agents>

[0641] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of generating alkali through physical or chemical action. Preferred alkali-generating agents for the resin composition of the present invention include thermal alkali-generating agents and photo-alkali-generating agents.

[0642] Among them, the alkali-generating agents that belong to the specific alkali-generating agents mentioned above are not the alkali-generating agents mentioned here.

[0643] In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali-generating agent. By containing a thermal alkali-generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, resulting in improved mechanical properties and chemical resistance of the cured product, and, for example, improved performance of the interlayer insulating film used as a rewiring layer in semiconductor packaging.

[0644] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from the base-generating agent include, for example, secondary and tertiary amines.

[0645] The alkali generating agent of the present invention is not particularly limited, and known alkali generating agents can be used. Examples of known alkali generating agents include, for instance, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimide compounds.

[0646] Specific compounds that can be cited as nonionic base generating agents include those represented by formula (B1), formula (B2), or formula (B3).

[0647] [Chemical Formula 48]

[0648]

[0649] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each of these can be an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Specifically, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2 and Rb3 None of them contain a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to this definition when the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0650] In equations (B1) and (B2), Rb is preferred. 1 、Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, more preferably at least two rings. The cyclic structure can be any of a monocyclic or fused ring, preferably a monocyclic or a fused ring formed by the condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0651] More specifically, Rb 1 and Rb 2 Preferably, the groups are hydrogen atoms, alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), or aralkyl groups (preferably 7-25 carbon atoms, more preferably 7-19, and even more preferably 7-12). These groups may have substituents within the range that allows the effects of the invention to be achieved. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are nitrogen-containing heterocycles of 4 to 7 members. Rb 1 and Rb 2 In particular, it is preferred to have a straight-chain, branched or cyclic alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12) that may have substituents, more preferably a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12) that may have substituents, and even more preferably a cyclohexyl group that may have substituents.

[0652] As Rb 3Examples of such compounds include alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-12, and even more preferably 2-6), aralkyl groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12), aryl-alkenyl groups (preferably 8-24 carbon atoms, more preferably 8-20, and even more preferably 8-16), alkoxy groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryloxy groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or arylalkoxy groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12). Among them, cycloalkyl (preferably 3-24 carbon atoms, more preferably 3-18, and even more preferably 3-12), aryl, and arylalkoxy are preferred. Rb 3 The invention may further contain substituents within the scope of achieving the effects of the invention.

[0653] The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

[0654] [Chemical Formula 49]

[0655]

[0656] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 respectively with Rb in equation (B1) 1 and Rb 2 They have the same meaning.

[0657] Rb 13 The groups are alkyl (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12), and may have substituents within the range that allows the effects of the present invention to be achieved. Rb 13 Preferably, it is an aryl alkyl group.

[0658] Rb 33 and Rb 34Each of the following is independently composed of hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen atoms.

[0659] Rb 35 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), and preferably aryl.

[0660] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

[0661] [Chemical Formula 50]

[0662]

[0663] Rb 11 and Rb 12 With Rb in equation (B1-1) 11 and Rb 12 They have the same meaning.

[0664] Rb 15 and Rb 16 The atom is a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0665] Rb 17 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), with aryl being the most preferred.

[0666] [Chemical Formula 51]

[0667]

[0668] In formula (B3), L represents a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the linking chain connecting adjacent oxygen and carbon atoms, indicating a hydrocarbon group with 3 or more atoms in the linking chain path. Furthermore, R... N1 and R N2 Each can be used to represent a monovalent organic group independently.

[0669] In this specification, a "linking chain" refers to an atomic chain along a path connecting two atoms or groups of atoms of the linked objects, where these linked objects are connected by the shortest (minimum number of atoms) distance. For example, in a compound represented by the following formula, L is composed of styrene, has vinyl as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms along the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "linking chain length") is 4.

[0670] [Chemical Formula 52]

[0671]

[0672] The number of carbon atoms in L of 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, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of enabling the above-mentioned intramolecular cyclization reaction to proceed rapidly, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more 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 examples of preferred compounds as base generating agents include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0673] Furthermore, the alkali generating agent preferably comprises a compound represented by the following formula (N1).

[0674] [Chemical Formula 53]

[0675]

[0676] In equation (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 The symbol represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0677] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0678] In equation (N1), R N1 and R N2 Each group independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include aliphatic hydrocarbon groups (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or aromatic hydrocarbon groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), preferably aliphatic hydrocarbon groups. As R N1 and R N2 If an aliphatic hydrocarbon group is used, the resulting base will have high basicity, which is preferred. Furthermore, the aliphatic and aromatic hydrocarbon groups can have substituents, and the aliphatic and aromatic hydrocarbon groups can also have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0679] As a component of R N1 and R N2 The aliphatic hydrocarbon group can be exemplified by straight-chain or branched chain alkyl groups, cyclic alkyl groups, combinations of chain alkyl and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. The number of carbon atoms in the straight-chain or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and even more preferably 3 to 12. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl.

[0680] The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0681] The number of carbon atoms in the group involved in the combination of chain alkyl and cyclic alkyl is preferably 4 to 24, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the groups involved in the combination of chain alkyl and cyclic alkyl include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0682] The alkyl group having oxygen atoms in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched.

[0683] From the perspective of increasing the boiling point of the alkali produced by the subsequent decomposition, R N1 and R N2 Preferably, the alkyl group has 5 to 12 carbon atoms. In formulations where adhesion to metal (e.g., copper) layers is important, the alkyl group having cyclic alkyl groups and 1 to 8 carbon atoms is preferred.

[0684] R N1 and R N2 They can link together to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, R... N1 and R N2 The formed ring structure can be a monocyclic ring or a fused ring, preferably a monocyclic ring. The formed ring structure is preferably a 5-membered or 6-membered ring containing a nitrogen atom from formula (N1), such as pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazoleidine rings, piperidine rings, piperazine rings, morpholine rings, etc., with pyrroleline rings, pyrrolidine rings, piperidine rings, piperazine rings, and morpholine rings being the most preferred.

[0685] R C1 This indicates a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0686] As a protecting group, a protecting group that decomposes by the action of an acid or base is preferred, and a protecting group that decomposes by an acid is a preferred example.

[0687] Specific examples of protecting groups include chain-like or cyclic alkyl groups or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl. Examples of chain-like alkyl groups having oxygen atoms in the chain include alkoxyalkyl groups, and more specifically, methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxacyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP)yl.

[0688] The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferred, more preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups preferably do not have an oxygen atom.

[0689] The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and even more preferably 2 to 6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The number of carbon atoms in the group (e.g., arylene alkyl) involved in the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0690] As the linking group L, specifically, preferably a linear or branched alkylene group, a cyclic alkylene group, a combination of linear and cyclic alkylene groups, an alkylene group having an oxygen atom in the chain, a linear or branched alkenyl group, a cyclic alkenyl group, an aryl group, or an aryl alkylene group.

[0691] The linear or branched alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

[0692] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6.

[0693] The number of carbon atoms in the groups involved in the combination of chain alkylene and cyclic alkylene is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0694] The alkylene group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. The number of carbon atoms in the alkylene group containing oxygen atoms in the chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0695] The number of carbon atoms in the linear or branched chain-like alkenyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0696] The cyclic alkenyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenyl group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2.

[0697] The number of carbon atoms in the arylene group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10.

[0698] The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.

[0699] Preferably, the compounds are chain-like alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain-like alkenyl, arylene, and arylene alkylene; more preferably, 1,2-vinyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and vinyloxyvinyl (especially 1,2-vinyloxy-1,2-vinyl).

[0700] Examples of alkali-generating agents can be given below, but the present invention should not be interpreted as limiting thereto.

[0701] [Chemical Formula 54]

[0702]

[0703] The molecular weight of the nonionic alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0704] Specific examples of preferred compounds as ionic base generators include, for instance, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0705] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

[0706] [Chemical Formula 55]

[0707]

[0708] Specific examples of imine salts include the following compounds, but the present invention is not limited to these.

[0709] [Chemical Formula 56]

[0710]

[0711] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent relative to 100 parts by weight of the resin in the resin composition of the present invention is preferably 0.1 to 50 parts by weight. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less, but can be 5 parts by weight or less, or 4 parts by weight or less.

[0712] One or more alkali-generating agents can be used. When two or more are used, the total dosage is preferably within the range mentioned above.

[0713] Solvent

[0714] The resin composition of the present invention preferably contains a solvent.

[0715] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0716] Examples of esters preferably 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.)). Alkyl esters of 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0717] Examples of ethers include, 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 acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0718] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0719] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0720] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0721] 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, and N-acetylmorpholine.

[0722] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0723] 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, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[0724] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0725] In this invention, a solvent preferably selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucanone, and dihydroL-glucanone, or a mixture of two or more solvents, is preferred. Particularly preferred are the combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate.

[0726] Regarding the solvent content, from the viewpoint of coatability, it is preferable to set the total solids concentration of the resin composition of the present invention to be 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the required coating thickness and coating method.

[0727] The resin composition of the present invention may contain only one solvent or two or more solvents. When containing two or more solvents, their total amount is preferably within the above-mentioned range.

[0728] <Metal Adhesion Modifier>

[0729] The resin composition of the present invention preferably contains a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilane groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0730] [Silane coupling agent]

[0731] Examples of silane coupling agents include, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573, all of which are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Moreover, the following compounds are preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0732] [Chemical Formula 57]

[0733]

[0734] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimeth ... Propyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0735] [Aluminum-based adhesive additives]

[0736] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0737] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are included in this specification.

[0738] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably in the range of 0.01 to 30 parts by weight, more preferably in the range of 0.1 to 10 parts by weight, and even more preferably in the range of 0.5 to 5 parts by weight. By setting the content above the lower limit, the adhesion between the pattern and the metal layer becomes better; by setting the content below the upper limit, the heat resistance and mechanical properties of the pattern become better. The metal adhesion modifier can be only one type or two or more types. When two or more types are used, their total content is preferably within the above range.

[0739] <Migration Inhibitors>

[0740] The resin composition of the present invention preferably further comprises a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0741] There are no particular limitations on the migration inhibitors, and examples include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds with thioalkyl groups, hindered phenolic compounds, salicylic acid derivatives, and hydrazide derivatives. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0742] Alternatively, ion trapping agents that capture anions such as halide ions can be used.

[0743] Other migration inhibitors include rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0744] The following compounds can be cited as specific examples of migration inhibitors.

[0745] [Chemical Formula 58]

[0746]

[0747] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0748] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, their total number is preferably within the range mentioned above.

[0749] <Polymerization Inhibitor>

[0750] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0751] Preferred compounds as polymerization inhibitors 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 salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, and 1-nitroso-2-naphthyl Phenol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenothiazine, phenazine, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, it is possible to use the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Patent Application Publication No. 2015 / 125469, which are incorporated herein by reference.

[0752] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0753] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, their total number is preferably within the range mentioned above.

[0754] Acid scavenger

[0755] In order to reduce the change in properties over time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Here, an acid scavenger is a compound that can capture the generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As an acid scavenger, compounds having an amino group are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are more preferred, primary amines, secondary amines, tertiary amines, and ammonium salts are even more preferred, and secondary amines, tertiary amines, and ammonium salts are particularly preferred.

[0756] Preferred acid scavengers include compounds having imidazole, diazabicyclic, ononium, trialkylamine, aniline, or pyridine structures; alkylamine derivatives having hydroxyl and / or ether bonds; and aniline derivatives having hydroxyl and / or ether bonds. When having an ononium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, iodine, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid with a lower acidity than the acid generated by the acid generator.

[0757] Examples of acid scavengers with an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers with a diazabicyclic structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undecyl-7-ene. Examples of acid scavengers with a onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, benzoylmethylsulfonium hydroxide, and sulfonium hydroxides with a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodine hydroxide, benzoylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Examples of acid scavengers with a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers with an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers with a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives with hydroxyl and / or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tri(methoxyethoxyethyl)amine. Examples of aniline derivatives with hydroxyl and / or ether bonds include N,N-bis(hydroxyethyl)aniline.

[0758] 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, and N-methylhexylamine. N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinyltriamine, diaminocyclohexyl, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamine ethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylene diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0759] These acid scavengers can be used alone or in combination of two or more.

[0760] The compositions of the present invention may or may not contain an acid scavenger, but when they do, the content of the acid scavenger is typically 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

[0761] The preferred ratio of acid generator to acid scavenger is an acid generator / acid scavenger molar ratio of 2.5 to 300. That is, considering sensitivity and resolution, a molar ratio of 2.5 or higher is preferred; considering the problem of resolution degradation caused by the coarsening of the relief pattern over time until the post-exposure heat treatment, a ratio of 300 or lower is preferred. An acid generator / acid scavenger molar ratio is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0762] <Other Additives>

[0763] The resin composition of the present invention can be incorporated with various additives as needed within the range of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the film properties and other properties can be adjusted. Regarding these components, for example, reference can be made to the descriptions after paragraph 0183 of Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, their total amount is preferably set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0764] [surfactants]

[0765] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0766] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially flowability) when preparing the coating liquid can be further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further improved. That is, when a film is formed using a coating liquid containing a surfactant composition, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating properties of the coated surface. Therefore, it is possible to form a film with less thickness variation and greater uniformity.

[0767] Examples of fluorinated surfactants include, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVASolutions Inc.), etc. Fluorinated surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, which are included in this specification. As a fluorinated surfactant, block polymers can also be used. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and these contents are incorporated into this specification.

[0768] Fluorinated surfactants may also preferably use fluorinated polymers (comprising repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propyleneoxy groups), and the following compounds may also be cited as fluorinated surfactants used in this invention.

[0769] [Chemical Formula 59]

[0770]

[0771] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0772] Regarding fluorinated surfactants, fluorinated polymers with olefinically unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DICCOporation.

[0773] The fluorine content in fluorinated surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniform coating thickness, liquid-saving properties, and good solubility in the composition.

[0774] Examples of silicone-based surfactants 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 Dow CorningToray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (manufactured by Shin-EtsuChemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0775] Examples of hydrocarbon-based surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FATCO., LTD).

[0776] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based 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 Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL&FAT CO., LTD.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., Ltd.), etc.

[0777] As cationic surfactants, examples include organosiloxane polymers such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers such as POLYFLOW No.75, No.77, No.90, and No.95 (manufactured by Kyoisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0778] As anionic surfactants, examples include WO04, WO05, WO17 (Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0779] Surfactants can be used in single-agent or in combination of two or more.

[0780] The surfactant content relative to the total solids content of the composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass.

[0781] [Higher fatty acid derivatives]

[0782] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoamide can be added to the resin composition of the present invention so that they are biased towards the surface of the resin composition of the present invention during the drying process after coating.

[0783] Furthermore, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0784] When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, their total content is preferably within the above-mentioned range.

[0785] [Thermal polymerization initiator]

[0786] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of polymerizable compounds. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be carried out, thereby further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiators sometimes also have the function of initiating polymerization by heat, and can sometimes be added as thermal polymerization initiators.

[0787] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated herein by reference, can be cited as thermal free radical polymerization initiators.

[0788] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0789] [Inorganic particles]

[0790] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0791] The average particle size of the aforementioned inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and especially preferably 0.04 to 0.5 μm.

[0792] The average particle size mentioned above is the primary particle size and is the volume average particle size. The volume average particle size can be measured by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.).

[0793] When the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0794] [Ultraviolet absorber]

[0795] The compositions of the present invention may contain ultraviolet absorbers. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.

[0796] Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, 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-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0797] Examples of acrylonitrile-based ultraviolet absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. Bis(hydroxyphenyl)triazine compounds such as 4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine.

[0798] In this invention, the various ultraviolet absorbers mentioned above can be used individually or in combination of two or more.

[0799] The composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition of the present invention 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.

[0800] [Organotitanium compounds]

[0801] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound, the resin composition can form a resin layer with excellent chemical resistance even when cured at low temperatures.

[0802] Examples of usable organotitanium compounds include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0803] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0804] I) Chelated titanium compounds: Among these, chelated titanium compounds having two or more alkoxy groups are more preferred, considering the excellent storage stability of the resin composition and the ability to obtain a good cured pattern. Specific examples include bis(triethanolamine)diisopropoxy titanium, bis(n-butoxy)bis(2,4-glutarate) titanium, diisopropoxybis(2,4-glutarate) titanium, diisopropoxybis(tetramethylheptanediate) titanium, and diisopropoxybis(ethyl acetoacetate) titanium.

[0805] II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc.

[0806] III) Titanium decene compounds: such as pentamethylcyclopentadienetrimethoxytitanium, 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-pyrrole-1-yl)phenyl)titanium, etc.

[0807] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecyl benzenesulfonate) isopropoxy titanium, etc.

[0808] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0809] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0810] VII) Titanate coupling agents: such as isopropyltris(2-dodecylbenzenesulfonyl)titanate, etc.

[0811] Among these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the above-mentioned I) chelated titanium compound, II) tetraalkoxy titanium compound, and III) dicarboxylated titanium compound is preferred as the organotitanium compound. Particularly preferred are diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium.

[0812] When an organotitanium compound is incorporated, the amount incorporated is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of a specific resin. When the amount incorporated is 0.05 parts by weight or more, the cured pattern obtained more effectively exhibits good heat resistance and chemical resistance; on the other hand, when it is 10 parts by weight or less, the composition exhibits better storage stability.

[0813] [Antioxidants]

[0814] The compositions of the present invention may contain antioxidants. By including antioxidants as additives, the tensile properties and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds are examples. Compounds having substituents at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above-mentioned substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, the antioxidant is also preferably a compound having a phenolic group and a phosphite group in the same molecule. Moreover, phosphorus-based antioxidants are also preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxophosphahepta-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphahepta-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants can also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Moreover, the compositions of the present invention may contain potential antioxidants as needed. Compounds that function as potential antioxidants include those whose antioxidant sites are protected by a protecting group, and whose protecting group is removed by heating at 100–250°C or at 80–200°C in the presence of an acid / base catalyst, thereby enabling them to function as antioxidants. Compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 are examples of potential antioxidants, and these contents are incorporated herein by reference. Commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKACORPORATION).

[0815] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0816] [Chemical Formula 60]

[0817]

[0818] In general formula (3), R 5 R represents an alkyl group having 2 or more hydrogen atoms or carbon atoms (preferably 2 to 10 carbon atoms). 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 It represents a 1- to 4-valent organic group containing at least one of an alkylene group, an oxygen atom, and a nitrogen atom with 2 or more carbon atoms (preferably 2 to 10 carbon atoms). k represents an integer from 1 to 4.

[0819] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups present in the resin. Moreover, it can inhibit metal oxidation by preventing rust on metallic materials.

[0820] In order to be effective on both resin and metal materials simultaneously, k is more preferably an integer from 2 to 4. As R 7 Examples of suitable groups include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and may further include substituents. From the viewpoint of solubility in the developer and metal adhesion, alkyl ethers and -NH- are preferred, and from the viewpoint of metal adhesion resulting from interaction with the resin and the formation of metal complexes, -NH- is more preferred.

[0821] Examples of compounds represented by general formula (3) include the following compounds, but are not limited to the following structures.

[0822] [Chemical Formula 61]

[0823]

[0824] [Chemical Formula 62]

[0825]

[0826] [Chemical Formula 63]

[0827]

[0828] [Chemical Formula 64]

[0829]

[0830] The amount of antioxidant added relative to 100 parts by weight of a specific resin is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain improved tensile properties and adhesion to metal materials even under high temperature and high humidity environments. Moreover, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, their sum and dosage are preferably within the above-mentioned range.

[0831] [Anticoagulant]

[0832] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0833] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination.

[0834] The composition of the present invention may or may not contain an anti-coagulant, but when it is contained, the content of the anti-coagulant relative to the total solid content of the composition of the present invention 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.

[0835] [Phenolic compounds]

[0836] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds 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 (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (trade names, manufactured by ASAHI YUKIZAI CORPORAT[ON]).

[0837] In this invention, phenolic compounds can be used alone or in combination of two or more.

[0838] The compositions of the present invention may or may not contain phenolic compounds, but when they are contained, the content of phenolic compounds relative to the total solid content of the compositions of the present invention 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.

[0839] [Other polymers]

[0840] Other examples of polymeric compounds include siloxane resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, phenolic varnish resins, methyl phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modifiers incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0841] In this invention, other polymer compounds can be used alone or in combination of two or more.

[0842] The composition of the present invention may or may not contain other polymeric compounds, but when it does contain other polymeric compounds, the content of other polymeric compounds relative to the total solid content of the composition of the present invention 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.

[0843] <Characteristics of Resin Compositions>

[0844] The viscosity of the resin composition of the present invention can be adjusted by the concentration of the solid components of the resin composition. From the viewpoint of coating film thickness, 1,000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, further preferably 2,500mm 2 / s~8,000mm 2 / s. As long as it remains within the above range, a highly uniform coating film can be easily obtained. For example, 1,000 mm. 2 At speeds above 12,000 mm, it is easy to apply the required film thickness for use as an insulating film for rewiring. 2 When the speed is below a certain value, a coating film with excellent surface finish can be obtained.

[0845] <Restrictions on substances contained in resin compositions>

[0846] The moisture 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 even more preferably less than 1.0% by mass. When it is less than 2.0%, the storage stability of the resin composition is improved.

[0847] Methods for maintaining moisture content include adjusting humidity in storage conditions and reducing the porosity of the storage container.

[0848] From the viewpoint of insulation, it is preferable that the metal content of the resin composition of the present invention is less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total amount of these metals is preferably within the above-mentioned range.

[0849] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials for forming the resin composition of the present invention, filtering the raw materials for forming the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0850] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The amount present as halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges.

[0851] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0852] As a container for the resin composition of the present invention, conventionally known containers can be used. Furthermore, for the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layered bottles with an inner wall composed of six types of six-layered resins, or bottles with a seven-layered structure formed by six types of resins, are preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0853] <Cure of the resin composition>

[0854] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0855] The cured product of the present invention is a cured product formed by curing the resin composition of the present invention.

[0856] The curing of the resin composition is preferably carried out by heating, with the heating temperature more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The morphology of the cured resin composition is not particularly limited, and it can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected according to applications such as forming a protective film on the wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, or imparting heat dissipation function. The film thickness of the cured product (the film formed by the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0857] The shrinkage rate of the resin composition of the present invention during curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated according to the following formula.

[0858] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0859] <Characteristics of cured resin compositions>

[0860] The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[0861] The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0862] The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0863] <Preparation of Resin Compositions>

[0864] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out using conventionally known methods.

[0865] Mixing can be carried out by stirring blades, by ball milling, or by rotating the tank itself.

[0866] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0867] Furthermore, for the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration is preferably performed using a filter. Regarding the filter pore size, for example, a pore size of 5 μm or less is preferred, 1 μm or less is more preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is even more preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be a filter that has been pre-cleaned with an organic solvent. In the filtration process, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, an HDPE filter with a pore size of 1 μm can be used as the first stage, and an HDPE filter with a pore size of 0.2 μm can be used as the second stage, and the two can be connected in series. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a circulating filtration. Furthermore, pressure filtration can be performed. When performing pressure filtration, for example, the applied pressure can be 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 even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0868] Besides using filters for filtration, adsorption materials can also be used for impurity removal. Furthermore, filtration and impurity removal using adsorption materials can be combined. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0869] After filtration, a further step can be performed whereby the resin composition filled in the bottle is placed under reduced pressure for degassing.

[0870] (Method for manufacturing solidified products)

[0871] The method for manufacturing the cured product of the present invention preferably includes a film forming step in which a resin composition is applied to a substrate to form a film.

[0872] Furthermore, the method for manufacturing the cured product of the present invention more preferably includes the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a developing step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[0873] The method for manufacturing the cured product of the present invention preferably includes at least one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[0874] Furthermore, the manufacturing method of the present invention preferably includes the above-described film formation step and the step of heating the above-described film.

[0875] The following is a detailed explanation of each process.

[0876] <Membrane Formation Process>

[0877] The resin composition of the present invention can be used in a film forming process suitable for forming a film on a substrate.

[0878] The method for manufacturing the cured product of the present invention preferably includes a film forming step in which a resin composition is applied to a substrate to form a film.

[0879] [Substrate]

[0880] The type of substrate can be appropriately determined according to the application. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any substrate formed of metal or substrates with metal layers formed by plating, vapor deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). There are no particular limitations. In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred.

[0881] Furthermore, layers such as an adhesion layer and an oxide layer formed of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[0882] Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular.

[0883] For the size of the substrate, when it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. When it is rectangular, the length of the shorter side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

[0884] Furthermore, as a substrate, a plate-like material can be used, with a panel-like substrate (substrate) being preferred.

[0885] Furthermore, when a resin composition is applied to the surface of a resin layer (e.g., a layer formed by curing) or a metal layer to form a film, the resin layer and the metal layer become substrates.

[0886] As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

[0887] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating are more preferred. From both the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0888] Furthermore, it is also possible to apply a method for transferring a coating film formed by pre-applying it to a temporary support through the above-described application method onto a substrate.

[0889] Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 is also preferred in this invention.

[0890] Furthermore, it can also perform a process to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinse (EBR) and back-side rinse.

[0891] Furthermore, the following pre-wetting process can also be used: before coating the resin composition onto the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0892] <Drying Process>

[0893] The above-mentioned membrane can be dried after the membrane formation process (layer formation process) to remove the solvent.

[0894] That is, the method for manufacturing the cured product of the present invention may include a drying step of drying the film formed by the film forming step.

[0895] Furthermore, the aforementioned drying process is preferably performed after the film formation process and before the exposure process.

[0896] The drying temperature of the membrane in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Furthermore, drying can be carried out under reduced pressure. Examples of drying times include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0897] <Exposure Process>

[0898] The above-mentioned film can undergo an exposure process that selectively exposes the film.

[0899] That is, the method for manufacturing the cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step.

[0900] Selective exposure refers to exposing only a portion of a film. Furthermore, by performing selective exposure, exposed areas (exposed regions) and unexposed areas (non-exposed regions) are formed on the film.

[0901] Regarding the exposure amount, there is no particular limitation as long as it is sufficient to cure the resin composition of the present invention. For example, based on the exposure energy at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ / cm. 2 More preferably 200–8,000 mJ / cm 2 .

[0902] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0903] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (three wavelengths of gamma, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, (7) second harmonic 532nm and third harmonic 355nm of YAG lasers, etc. For the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is even more preferred. This results in particularly high exposure sensitivity.

[0904] Moreover, the exposure method is not particularly limited, as long as at least a portion of the film formed by the resin composition of the present invention is exposed, such as exposure using a photomask, exposure based on laser direct imaging, etc.

[0905] <Post-exposure heating process>

[0906] The above-mentioned film can undergo a heating process after exposure (post-exposure heating process).

[0907] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

[0908] The post-exposure heating process can be performed after the exposure process and before the development process.

[0909] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0910] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0911] Regarding the heating rate in the post-exposure heating process, it is preferably 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0912] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0913] There are no particular limitations on the heating method used in the post-exposure heating process; known heating plates, ovens, infrared heaters, etc., can be used.

[0914] Furthermore, heating is preferably carried out in an atmosphere with low oxygen concentration by circulating inert gases such as nitrogen, helium, or argon.

[0915] <Developing Process>

[0916] The exposed film can be developed using a developing solution to form a pattern.

[0917] That is, the method for manufacturing the cured product of the present invention may include a developing step of developing a film exposed by an exposure step to form a pattern using a developing solution.

[0918] By developing the film, one of the exposed and unexposed portions is removed to form a pattern.

[0919] Here, the development process that removes the non-exposed parts of the film is called negative development, and the development process that removes the exposed parts of the film is called positive development.

[0920] [Developing solution]

[0921] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0922] When the developer is an alkaline aqueous solution, examples include inorganic bases, 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, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, piperidine, and more preferably TMAH. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass of the total amount of developer, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0923] When the developer contains an organic solvent, esters are preferably included, 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., 3-alkyl...). Methyl hydroxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably 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., etc. Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of preferred sulfoxides include dimethyl sulfoxide; examples of preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0924] Furthermore, when the developer contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred; a developer containing at least one selected from cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred; and a developer containing cyclopentanone is most preferred.

[0925] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content can also be 100% by mass.

[0926] Developer solutions may also contain other ingredients.

[0927] Other components include, for example, well-known surfactants and well-known defoamers.

[0928] [Method for supplying developer]

[0929] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include: immersing the substrate with the film formed in the developer; swirling immersion development using a nozzle to supply the developer to the film formed on the substrate; or continuous supply of developer. There are no particular restrictions on the type of nozzle; examples include direct-flow nozzles, spray nozzles, and atomizing nozzles.

[0930] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to supply the developer using a direct current nozzle or a continuous supply method using a spray nozzle. From the viewpoint of developer penetration into the image area, a spray nozzle supply method is more preferred.

[0931] Furthermore, the following process can be adopted: after continuously supplying developer with a DC nozzle, rotating the substrate to remove developer from the substrate, rotating and drying, and then continuously supplying developer with a DC nozzle again, rotating the substrate to remove developer from the substrate, or repeating this process multiple times.

[0932] Furthermore, as a method for supplying developer in the developing process, one can employ a process of continuously supplying developer to the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer on the substrate using ultrasound or the like, and a process combining these methods.

[0933] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution is not particularly limited, but it is preferably performed at 10 to 45°C, and more preferably at 18 to 30°C.

[0934] During the developing process, the pattern can be further cleaned (rinsed) with a rinsing solution after treatment with the developing solution. Furthermore, methods such as supplying the rinsing solution before the developing solution in contact with the pattern has completely dried can also be employed.

[0935] [Rinse solution]

[0936] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0937] When the rinsing solution contains an organic solvent, preferred organic solvents include, for example, esters such as 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3-alkoxy...). Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-alkoxy-2-methylpropionate) Methyl acetoacetate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably 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., etc. Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of preferred sulfoxides include dimethyl sulfoxide; examples of preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0938] When the rinsing solution contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0939] When the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains at least 50% by mass of an organic solvent, more preferably at least 70% by mass, and even more preferably at least 90% by mass. Moreover, the rinsing solution may contain 100% by mass of an organic solvent.

[0940] The rinsing solution may also contain other ingredients.

[0941] Other components include, for example, well-known surfactants and well-known defoamers.

[0942] [Method for supplying flushing fluid]

[0943] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. The following methods are available: immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by swirling and immersion, supplying the rinsing liquid to the substrate by spraying a nozzle, or continuously supplying the rinsing liquid to the substrate by a direct current nozzle.

[0944] From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, methods for supplying rinsing fluid include spray nozzles, direct current nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred. From the perspective of the penetrability of the rinsing fluid to the image area, a mist nozzle supply method is even more preferred. There are no particular limitations on the type of nozzle; examples include direct current nozzles, spray nozzles, and mist nozzles.

[0945] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed film via a DC nozzle, and more preferably a process of supplying rinsing liquid via a spray nozzle.

[0946] Furthermore, as a method for supplying rinsing fluid in the rinsing process, one can employ a process of continuously supplying rinsing fluid to the substrate, a process of keeping the rinsing fluid on the substrate in a substantially static state, a process of vibrating the rinsing fluid on the substrate using ultrasound or the like, and a process combining these methods.

[0947] The preferred rinsing time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly limited, but it is preferably performed at 10 to 45°C, more preferably at 18 to 30°C.

[0948] <Heating Process>

[0949] The pattern obtained through the developing process (or the washed pattern if a washing process is performed) can be subjected to a heating process that heats the pattern obtained through the developing process.

[0950] That is, the method for manufacturing the cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.

[0951] Furthermore, the method for manufacturing the cured product of the present invention may include a heating step of heating a pattern obtained by other methods without a developing step or a film obtained by a film forming step.

[0952] During the heating process, resins such as polyimide precursors cyclize into resins such as polyimide.

[0953] Furthermore, it also involves crosslinking unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins.

[0954] The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, and even more preferably 160 to 250°C, especially preferably 160 to 230°C.

[0955] The heating process is preferably a process in which the cyclization reaction of the polyimide precursor is promoted within the pattern by means of the alkali or the like generated from the alkali generating agent through heating.

[0956] Regarding the heating process, the heating is preferably performed at a rate of 1 to 12°C / minute from the initial temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, productivity can be ensured while preventing excessive evaporation of acid or solvent; by setting the heating rate to 12°C / minute or less, residual stress in the cured product can be mitigated.

[0957] Furthermore, in the case of an oven capable of rapid heating, the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0958] The initial heating temperature is preferably 20–150°C, more preferably 20–130°C, and even more preferably 25–120°C. The initial heating temperature refers to the temperature at which the process begins when the material is heated to the maximum heating temperature. For example, in the case of applying the resin composition of the present invention to a substrate and then drying it, the temperature of the dried film (layer) is preferred; for example, it is preferably started at a temperature 30–200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0959] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0960] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher.

[0961] The upper limit of the above temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

[0962] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / min and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C / min and holding at 180°C for 120 minutes. Furthermore, it is preferable to perform the treatment while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such pretreatment steps can improve the properties of the membrane. The pretreatment steps are preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be a two-stage or more process; for example, the first stage of the pretreatment step can be performed in the range of 100–150°C, and then the second stage of the pretreatment step can be performed in the range of 150–200°C.

[0963] Furthermore, cooling can be performed after heating, and the preferred cooling rate at this time is 1 to 5°C / minute.

[0964] Regarding the heating process, to prevent the decomposition of specific resins, it is preferable to carry it under reduced pressure using inert gases such as nitrogen, helium, or argon, thereby creating an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0965] There are no particular limitations on the heating method used in the heating process; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0966] <Post-development exposure process>

[0967] The pattern obtained through the developing process (or the washed pattern in the case of a washing process) can replace the heating process described above, or, in addition to the heating process described above, be exposed to the pattern after the developing process via a post-developing exposure process.

[0968] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for manufacturing the 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.

[0969] In the post-development exposure process, reactions such as cyclization of polyimide precursors by exposure to photoalkali generating agents and removal of acid-decomposing groups by exposure to photoacid generating agents can be promoted.

[0970] In the post-development exposure process, at least a portion of the pattern obtained in the development process needs to be exposed, preferably all of the pattern is exposed.

[0971] Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure process is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[0972] Regarding the post-development exposure process, for example, the light source used in the above-mentioned exposure process can be used, and broadband light is preferred.

[0973] <Metal Layer Formation Process>

[0974] The pattern obtained through the development process (preferably at least one of the heating process and the post-development exposure process) can be used for a metal layer forming process to form a metal layer on the pattern.

[0975] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably at least one of a heating step and a post-developing exposure step).

[0976] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are preferred, and copper is even more preferred.

[0977] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 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, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electroplating can be cited. As a preferred method of plating, electroplating using copper sulfate plating solution and copper cyanide plating solution can be cited.

[0978] The thickness of the metal layer, measured in the thickest part, is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

[0979] <Application>

[0980] Examples of applications applicable to the manufacturing method of the cured product of the present invention or to the cured product of the present invention include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress-relief films. Other examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or patterns formed on insulating films used in practical mounting applications of the above types by etching. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimide,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide & Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0981] Furthermore, the method for manufacturing the cured product of the present invention or the cured product of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, the use of forming parts in etching, and the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0982] (Laminated bodies and methods for manufacturing laminated bodies)

[0983] The laminate of the present invention refers to a structure having multiple layers formed by the cured product of the present invention.

[0984] The laminate of the present invention is a laminate containing two or more layers formed by a cured material, or it can be a laminate consisting of three or more layers.

[0985] Of the two or more layers formed by the cured material included in the above-mentioned laminate, at least one layer is formed by the cured material of the present invention. From the viewpoint of suppressing the shrinkage of the cured material or the deformation of the cured material that accompanies the shrinkage, it is even more preferable that all the layers formed by the cured material included in the above-mentioned laminate are formed by the cured material of the present invention.

[0986] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the cured product of the present invention, and more preferably includes the steps of repeating the method for manufacturing the cured product of the present invention multiple times.

[0987] The laminate of the present invention comprises two or more layers formed of a cured material, preferably in which any layer formed of the cured material contains a metal layer between them. The metal layer is preferably formed by the metal layer forming process described above.

[0988] That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step between multiple methods for manufacturing cured products, wherein a metal layer is formed on the layer formed by the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0989] As an example of the aforementioned laminate, a laminate structure comprising at least three layers sequentially stacked: a layer formed of a first cured material, a metal layer, and a layer formed of a second cured material is preferred.

[0990] Both the layer formed by the first cured product and the layer formed by the second cured product are preferably layers formed by the cured products of the present invention. The resin composition of the present invention used to form the layer formed by the first cured product and the resin composition of the present invention used to form the layer formed by the second cured product may be the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0991] <Layering Process>

[0992] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0993] The lamination process includes a series of steps on the surface of a pattern (resin layer) or metal layer, sequentially performing at least one of the following steps: (a) film formation (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step. This can be achieved by repeating at least one of (a) film formation step, (d) heating step, and post-development exposure step. Furthermore, (e) metal layer formation step can be included after at least one of (d) heating step and post-development exposure step. The lamination process can obviously be further appropriately included with steps such as the aforementioned drying step.

[0994] When performing a further lamination process after the lamination process, a surface activation treatment process can be performed after the aforementioned exposure process, the aforementioned heating process, or the aforementioned metal layer formation process. Plasma treatment is an example of a surface activation treatment. Details regarding surface activation treatment will be explained later.

[0995] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0996] For example, a structure with 2 or more but less than 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure with 2 or more but less than 9 layers is even more preferred.

[0997] The composition, shape, and film thickness of the above layers can be the same or different.

[0998] In this invention, it is preferable to further form a cured resin composition (resin layer) of the present invention to cover the metal layer, particularly after the metal layer is formed. Specifically, examples include repeating at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order, or repeating at least one of (a) film formation step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order. By alternately performing the lamination step of the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[0999] (Surface activation treatment process)

[1000] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer.

[1001] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the development process (preferably after at least one of the heating process and the post-development exposure process) or after the surface activation treatment process of the resin composition layer.

[1002] The surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, the surface activation treatment is performed on at least a portion of the metal layer, and more preferably on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. Thus, by performing a surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved.

[1003] Furthermore, the surface activation treatment is preferably performed on part or all of the exposed resin composition layer (resin layer). In this way, by performing surface activation treatment on the surface of the resin compo...

Claims

1. A resin composition comprising: Nonionic base-generating agents that produce bases with pyridine structures through the action of light or heat; Precursors to cyclized resins; and Photoradical polymerization initiator The precursor of the cyclized resin is at least one resin selected from polyimide precursor, polybenzoxazole precursor, and polyamide-imide precursor. The resin has free radical polymerizable groups. The content of the cyclized resin precursor is 20% by mass or more and 99.5% by mass or less relative to the total solids content of the resin composition, and the content of the nonionic alkali generating agent is 0.5% by mass or more and 20% by mass or less relative to the total solids content of the resin composition. The nonionic base generating agent is a compound represented by formula (1-1) or formula (1-2) below. In equation (1-1), L 1 R represents an n+m valence linkage group. 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them are optionally bonded to form a ring structure, where X independently represents a hydroxyl or carboxyl group, n represents an integer from 1 to 4, and m represents an integer from 1 to 4. In equation (1-2), L 2 and L 3 Each can independently represent a single bond or a divalent linked group; Ar represents an aromatic group optionally having a substituent; R 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them are optionally bonded to form a ring structure, where X independently represents a hydroxyl or a carboxyl group, x represents an integer from 1 to 4, and y represents an integer from 1 to 4.

2. A resin composition comprising: Nonionic base-generating agents that produce bases with pyridine structures through the action of light or heat; Precursors to cyclized resins; and Photoacid generator, The precursor of the cyclized resin is at least one resin selected from polyimide precursor, polybenzoxazole precursor, and polyamide-imide precursor. The resin has acid-decomposable groups. The content of the cyclized resin precursor is 20% by mass or more and 99.5% by mass or less relative to the total solids content of the resin composition, and the content of the nonionic alkali generating agent is 0.5% by mass or more and 20% by mass or less relative to the total solids content of the resin composition. The nonionic base generating agent is a compound represented by formula (1-1) or formula (1-2) below. In equation (1-1), L 1 R represents an n+m valence linkage group. 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them are optionally bonded to form a ring structure, where X independently represents a hydroxyl or carboxyl group, n represents an integer from 1 to 4, and m represents an integer from 1 to 4. In equation (1-2), L 2 and L 3 Each can independently represent a single bond or a divalent linked group; Ar represents an aromatic group optionally having a substituent; R 2 ~R 6 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 2 ~R 6 At least two of them are optionally bonded to form a ring structure, where X independently represents a hydroxyl or a carboxyl group, x represents an integer from 1 to 4, and y represents an integer from 1 to 4.

3. The resin composition according to claim 1, wherein it comprises a polymerizable compound.

4. The resin composition according to any one of claims 1 to 3, used for forming an interlayer insulating film for a rewiring layer.

5. A cured product formed by curing the resin composition according to any one of claims 1 to 4.

6. A laminate comprising two or more layers formed from the cured material of claim 5, wherein any layer formed from the cured material comprises a metal layer between each other.

7. A method for manufacturing a cured product, comprising a film forming step of applying the resin composition of any one of claims 1 to 4 to form a film on a substrate.

8. The method for manufacturing a cured material according to claim 7, comprising an exposure step of selectively exposing the film and a development step of developing the film using a developing solution to form a pattern.

9. The method for manufacturing a cured material according to claim 7, comprising a heating step of heating the film at 50°C to 450°C.

10. A semiconductor device comprising the cured material of claim 5.

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