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

Abstract

The present application provides a resin composition, a cured product obtained by curing the above composition and a manufacturing method thereof, a laminate containing the cured product and a manufacturing method thereof, a semiconductor device and a manufacturing method thereof, and a novel resin, the resin composition having a polyamide acid having a structure represented by at least one of the following formula (P-1) and the following formula (P-2) and a photoradical polymerization initiator; in formula (P-1), R P1 represents a monovalent organic group, n represents an integer of 0 to 4, and * represents a bonding site with other structures, and in formula (P-2), R P2 each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures.

Description

Technical Field

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

[0002] Today, resin materials made from resin compositions containing resins are being used in various fields.

[0003] For example, heterocyclic polymers such as polyimide are used in a variety of applications due to their excellent heat resistance and insulation properties. There are no particular limitations to these applications; for example, in the case of mounting semiconductor devices, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can also be used as base films or coverlays for flexible substrates.

[0004] For example, in the above-described applications, heterocyclic polymers such as polyimides are used as resin compositions containing polyimide precursors such as polyamic acid.

[0005] For example, this resin composition is applied to a substrate by coating to form a photosensitive film, and then exposed, developed, heated, etc., as needed to form a cured product on the substrate.

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application location of the resin composition. From the perspective of this excellent manufacturing adaptability, in addition to the high performance inherent in heterocyclic polymers such as polyimide, the industrial applications of the aforementioned resin composition are increasingly anticipated.

[0007] For example, Patent Document 1 describes a polyimide resin and a varnish composition comprising the polyimide resin and an organic solvent, wherein the polyimide resin has a molecular chain containing specific constituent units and the molecular chain contains free radical polymerizable groups or cationic polymerizable groups.

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: International Publication No. 2022-073127 Summary of the Invention

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

[0012] In cured products containing polyimide, as wiring patterns become finer, there is a need to suppress defects by using components that do not easily expand as resin-containing components.

[0013] Therefore, it is sometimes required that a cured product with a low coefficient of thermal expansion be obtained in a resin composition containing polyamic acid.

[0014] The object of the present invention is to provide a resin composition that can produce a cured product with a small coefficient of thermal expansion, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device including the cured product.

[0015] Furthermore, the purpose of this invention is to provide a novel resin.

[0016] means for solving technical problems

[0017] The following are examples of representative embodiments of the present invention.

[0018] <1> A resin composition comprising:

[0019] Polyamic acid, having at least one of the structures selected from the group consisting of the structure represented by formula (P-1) and the structure represented by formula (P-2); and

[0020] Photoradical polymerization initiator.

[0021] [Chemical Formula 1]

[0022]

[0023] In equation (P-1), R P1 The symbol represents a monovalent organic group, n represents an integer from 0 to 4, and * represents a bonding site with other structures.

[0024] In equation (P-2), R P2 Each symbol represents a hydrogen atom or a monovalent organic group independently, and * indicates a bonding site with other structures.

[0025] <2> The resin composition according to <1>, wherein,

[0026] The polyamic acid described above contains repeating units represented by the following formula (1-1).

[0027] [Chemical Formula 2]

[0028]

[0029] In equation (1-1), X 2Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 3 and R 4 Each of the following expressions (R-1) represents the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

[0030] [Chemical Formula 3]

[0031]

[0032] In equation (R-1), L 1 A represents a linker base with valence a1+1. 1 This represents the structure indicated by equation (P-1) or (P-2) above, where a1 represents an integer greater than or equal to 1, and * represents the structure related to X in equation (1-1). 2 Or Y 2 The bonding sites.

[0033] <3> The resin composition according to <2>, wherein,

[0034] The above-mentioned polyamic acid comprises the structure represented by the following formula (2-1) or the following formula (2-2).

[0035] [Chemical Formula 4]

[0036]

[0037] In equations (2-1) and (2-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 Each independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, V 1 Z represents a linker base that is either a single bond or divalent. 1 Q represents the amino group that can be protected. 1 R represents a structure containing a protected carboxyl group. 3 R 4 Each of the above formulas (R-1) can be used to represent the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

[0038] <4> The resin composition according to any one of <1> to <3> further comprises a resin that is different from the above-described polyamic acid and comprises repeating units represented by the following formula (3-1).

[0039] [Chemical Formula 5]

[0040]

[0041] In equation (3-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of the following expressions (R-2) can be used to independently represent the structure represented by m, where m represents an integer from 0 to 4 and n represents an integer greater than or equal to 1.

[0042] [Chemical Formula 6]

[0043]

[0044] In equation (R-2), L 2 A represents a linker basis with a valence of a²+1. 2 The symbol represents a polymerizable group, a2 represents an integer greater than or equal to 1, and * represents X in equation (3-1). 1 Or Y 1 The bonding sites.

[0045] <5> The resin composition according to <4>, wherein,

[0046] A in equation (R-2) included in equation (3-1) 2 At least one of them is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl or a group containing these.

[0047] <6> The resin composition according to <4>, wherein,

[0048] In equation (3-1), A in equation (R-2) 2 At least one of them is vinylphenyl.

[0049] <7> The resin composition according to any one of <1> to <6> further comprises a polymerizable compound.

[0050] <8> The curable resin composition according to any one of <1> to <7> further comprises an azole compound and a silane coupling agent.

[0051] <9> The resin composition according to any one of <1> to <8> comprises a solvent having a boiling point of 100 to 260°C.

[0052] <10> The resin composition according to <9>, wherein,

[0053] The content of the solvent with a boiling point of 100 to 260°C is 40% by mass or more relative to the total mass of the composition.

[0054] <11> The resin composition according to <9> contains two or more solvents with boiling points of 100 to 260°C.

[0055] <12> The resin composition according to any one of <1> to <11> is used to form an interlayer insulating film for a rewiring layer.

[0056] <13> A cured product formed by curing any one of the resin compositions <1> to <12>.

[0057] <14> A laminate comprising two or more layers formed of the cured material described in <13>, and including a metal layer between any of the layers formed of the cured material.

[0058] <15> A method for manufacturing a cured material, the method comprising a film forming step of applying a resin composition as described in any one of <1> to <12> onto a substrate to form a film.

[0059] <16> The method for manufacturing the cured material according to <15> includes an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.

[0060] <17> The method for manufacturing the cured material according to <15> or <16> includes a heating step of heating the film at 50 to 450°C.

[0061] <18> A method for manufacturing a laminate, the method comprising the method for manufacturing a cured material as described in any one of <15> to <17>.

[0062] <19> A method for manufacturing a semiconductor device, the method comprising the method for manufacturing a cured material as described in any one of <15> to <17>.

[0063] <20> A semiconductor device comprising the cured material described in <13>.

[0064] <21> A resin comprising repeating units represented by the following formula (1-1).

[0065] [Chemical Formula 7]

[0066]

[0067] In equation (1-1), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 3 and R 4 Each of the following expressions (R-1) represents the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

[0068] [Chemical Formula 8]

[0069]

[0070] In equation (R-1), L 1 A represents a linker base with valence a1+1. 1 The structure represented by equation (P-1) or (P-2) is given, where a1 represents an integer greater than 1, and * represents the structure related to X in equation (1-1). 1 Or Y 1 The bonding sites.

[0071] [Chemical Formula 9]

[0072]

[0073] In equation (P-1), R P1 The symbol represents a monovalent organic group, n represents an integer from 0 to 4, and * represents the L in formula (R-1). 1 The bonding sites.

[0074] In equation (P-2), R P2 Each of the above represents a hydrogen atom or a monovalent organic group independently, and * indicates a group related to L in formula (R-1). 1 The bonding sites.

[0075] <22> According to the resin described in <21>, wherein,

[0076] The content of free radical polymerizable groups in the above resin is 0.5 mmol / g or more.

[0077] <23> According to the resin described in <21> or <22>, wherein,

[0078] The above-mentioned resin contains the structure represented by (2-1) or (2-2) below.

[0079] [Chemical Formula 10]

[0080]

[0081] In equations (2-1) and (2-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R2 Each independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, V 1 Z represents a linker base that is either a single bond or divalent. 1 Q represents the amino group that can be protected. 1 R represents a structure containing a protected carboxyl group. 3 R 4 Each of the above formulas (R-1) can be used to represent the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

[0082] Invention Effects

[0083] According to the present invention, a resin composition that yields a cured product with a low coefficient of thermal expansion is provided, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product are provided.

[0084] Furthermore, according to the present invention, a novel resin is provided. Detailed Implementation

[0085] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0086] In this specification, the numerical range indicated by the symbol “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0087] In this specification, the term "process" refers not only to independent processes, but also to processes that cannot be clearly distinguished from other processes, as long as the expected function of the process can be achieved.

[0088] In the description of "base" (atomic group) in this specification, the descriptions without "substituted" and "unsubstituted" include bases (atomic groups) that do not have substituents, and also include bases (atomic groups) that have substituents. For example, "alkyl" includes not only alkyl groups that do not have substituents (unsubstituted alkyl groups), but also alkyl groups that have substituents (substituted alkyl groups).

[0089] In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used in 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 photochemical rays or radiation.

[0090] In this specification, "(meth)acrylate" means either "acrylate" or "methacrylate", "(meth)acrylic acid" means either "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" means either "acryloyl" or "methacryloyl".

[0091] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0092] In this specification, total solids content refers to the total mass of the components obtained after removing the solvent from all components of the composition. 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.

[0093] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel permeation chromatography (GPC) and are defined as polystyrene equivalents. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) and connecting guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) in series as columns. These molecular weights are determined using NMP (N-methyl-2-pyrrolidone) as the eluent, unless otherwise specified. In cases where NMP is unsuitable as an eluent due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, regarding the detection in GPC measurements, unless otherwise specifically stated, a UV (ultraviolet) detector with a wavelength of 254 nm is used.

[0094] In this specification, the positional relationship of the layers constituting the laminate is referred to as "upper" or "lower" simply as long as there are other layers above or below the reference layer among the layers of interest. That is, a third layer or element may be further inserted between the reference layer and the other layers, without the reference layer needing to be in contact with the other layers. Unless otherwise specified, the direction of the stacked layers relative to the substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, this vertical direction is provided for ease of explanation in this specification; in practice, the "upper" direction in this specification may differ from vertically upward.

[0095] In this specification, unless otherwise specified, each component included in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0096] Unless otherwise specified, the temperature in this specification is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0097] In this specification, the preferred combination of methods is a more preferred method.

[0098] (Resin composition)

[0099] The resin composition of the present invention comprises a polyamic acid having at least one of the structures represented by formula (P-1) and formula (P-2) and a photoradical polymerization initiator.

[0100] Hereinafter, polyamic acid having at least one of the structures represented by formula (P-1) and formula (P-2) will also be referred to as "specific resin".

[0101] The resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and more preferably to form a film for exposure and development using a developer containing an organic solvent.

[0102] 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.

[0103] In particular, using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer is also one of the preferred embodiments of the present invention.

[0104] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative development.

[0105] In this invention, negative development refers to the development of non-exposed areas by developing during exposure and development, while positive development refers to the development of exposed areas by developing.

[0106] The exposure method, the developer, and the development method described above can be, for example, the exposure method described in the exposure step, the developer described in the development step, and the development method described in the following description of the method for manufacturing cured material.

[0107] According to the resin composition of the present invention, a cured product with a small coefficient of thermal expansion (CTE) can be obtained.

[0108] The mechanism by which the above effects are achieved is not yet clear, but the following is a hypothesis.

[0109] In polyamic acids having at least one of the structures represented by formula (P-1) and the structure represented by formula (P-2) below, the vinylphenyl or maleimide groups contained in these structures have excellent solvent solubility. Therefore, by introducing a rigid structure that is effective in reducing the CTE of the resin into the main chain structure, the CTE of the membrane can be reduced.

[0110] Furthermore, by having the aforementioned vinylphenyl or maleimide groups in the resin, both solvent solubility and exposure-based free radical crosslinking can be achieved, thus enabling light-based patterning with excellent resolution.

[0111] Furthermore, polyamic acid is imidized through thermosetting, but during imidization, large molecular weight groups, such as polyamic acid esters with polymerizable groups, do not detach, resulting in low volatile content and difficulty in film shrinkage, thus making curing shrinkage difficult.

[0112] In addition, it is believed that by endowing polyamic acid with amino or carboxylic acid and its derivatives, the molecular weight can be increased during heat curing, and the elongation at break can be improved.

[0113] Furthermore, it is believed that by using polyimides with polymerizable groups, volatile components are further reduced, thus further suppressing curing shrinkage. It is also believed that the proportion of imides in the resin of the film can be increased, thus becoming advantageous for the CTE or elongation at break of the cured film.

[0114] Furthermore, polyamic acid undergoes ring closure (imidization) through heat curing, where water or alcohols with 4 or fewer carbon atoms are released. These waters or alcohols have low boiling points, making it difficult for them to remain in the cured film, resulting in a very low alcohol content. Consequently, it is believed that during insulation reliability tests under high temperature and high humidity conditions, moisture is less likely to penetrate the cured material, thus inhibiting resin decomposition. Furthermore, it is believed that the low CTE, as described above, leads to high resin orientation in the film. It is speculated that through these synergistic effects, a cured material with excellent insulation reliability can be obtained.

[0115] Here, Patent Document 1 does not describe a resin composition containing a resin corresponding to a specific resin.

[0116] The components contained in the resin composition of the present invention will be described in detail below.

[0117] <Specific Resins>

[0118] The resin composition of the present invention comprises a polyamic acid (specific resin) having at least one of the structures selected from the group consisting of the structure represented by the following formula (P-1) and the structure represented by the following formula (P-2).

[0119] [Chemical Formula 11]

[0120]

[0121] In equation (P-1), R P1 The symbol represents a monovalent organic group, n represents an integer from 0 to 4, and * represents a bonding site with other structures.

[0122] In equation (P-2), R P2 Each symbol represents a hydrogen atom or a monovalent organic group independently, and * indicates a bonding site with other structures.

[0123] [Polyamic acid]

[0124] In this invention, polyamic acid refers to a resin containing repeating units having a structure comprising -CONH- and -COOR (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom), and whose chemical structure of the -CONH- and -COOR changes to become an imide group through external stimulation.

[0125] The aforementioned changes in chemical structure are preferably caused by heat.

[0126] Furthermore, polyamic acid is more preferably a resin that forms an imide ring structure through a heat-induced ring-closing reaction to become a polyimide.

[0127] In this invention, polyimide refers to a resin having repeating units containing imide groups within its molecular chain, preferably a resin having repeating units containing imide ring structures within its molecular chain.

[0128] Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having repeating units containing imide groups in the main chain, and more preferably a resin having repeating units containing imide ring structures in the main chain.

[0129] In this specification, "main chain" refers to the longest bonded chain in the resin molecule, and "side chain" refers to all other bonded chains.

[0130] In this specification, the imide group refers to the structure represented by *-C(=O)N(-*)C(=O)-*, where * indicates a bonding site with other structures, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom.

[0131] In this specification, an imide ring structure refers to a ring structure in which both carbon atoms and nitrogen atoms of the aforementioned imide are used as ring-forming atoms. The imide ring structure is preferably a 5-membered ring.

[0132] Polyimide can be a so-called polyamide-imide, which has amide groups in addition to imide groups within its molecular chain. In this specification, the amide group refers to the structure represented by *-C(=O)N(-#)-*, where * indicates a bonding site with other structures, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Furthermore, # indicates a bonding site with other structures, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0133] In equation (P-1), R is... P1 Examples include alkyl and aryl groups.

[0134] In formula (P-1), n ​​is preferably 0 or 1, and more preferably 0.

[0135] In formula (P-1), * is preferably present at the para position of the vinyl group.

[0136] In equation (P-2), R P2 Preferably, each is an independent hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0137] The total content of the structure represented by formula (P-1) and the structure represented by formula (P-2) in the specific resin is preferably 0.2 to 5.0 mmol / g, more preferably 0.25 to 4.0 mmol / g, and even more preferably 0.5 to 3.0 mmol / g.

[0138] For example, the content of the structure represented by formula (P-1) in the resin of the composition can be calculated by the following method.

[0139] Add 1g of the composition to 50g of methanol or water to induce crystallization, allowing the specific resin to precipitate and then filter. Recover the filtrate and dissolve it in 3.0g of THF (tetrahydrofuran), add it to 50g of methanol or water to induce crystallization, filter, and dry at 40°C for 20 hours.

[0140] After dissolving 0.1 g of the specific resin dried above in 0.9 g of deuterated dimethyl sulfoxide (DMSO), it was then... 1 The amount of vinylphenyl was determined by H-NMR. 1 The cumulative number of H-NMR measurements was set to 640.

[0141] For example, tetramethylsilane can be used as a reference material, and according to 1The molar amount of the structure represented by formula (P-1) in the specific resin is calculated by the ratio of the integrated intensity of the peak near 5.0 to 7.0 ppm derived from vinylphenyl in the H-NMR spectrum to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specific resin mentioned above.

[0142] The molar amounts of other structures can also be determined by calculating the integral intensity of the peak values ​​corresponding to each structure.

[0143] The content of free radical polymerizable groups in the specific resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and even more preferably 0.8 mmol / g or more.

[0144] The above-mentioned content is preferably 5.0 mmol / g or less, more preferably 4.0 mmol / g or less, and even more preferably 3.0 mmol / g or less.

[0145] [Equation (1-1)]

[0146] Polyamic acid preferably contains repeating units represented by the following formula (1-1).

[0147] [Chemical Formula 12]

[0148]

[0149] In equation (1-1), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 3 and R 4 Each of the following expressions (R-1) represents the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

[0150] [Chemical Formula 13]

[0151]

[0152] In equation (R-1), L 1 A represents a linker base with valence a1+1. 1 This represents the structure indicated by equation (P-1) or (P-2) above, where a1 represents an integer greater than or equal to 1, and * represents the structure related to X in equation (1-1). 2 Or Y 2 The bonding sites.

[0153] -R 1 and R 2 -

[0154] In equation (1-1), R 1 and R 2 Ideally, all atoms should be hydrogen atoms.

[0155] -X 2 -

[0156] X 2 The carbon number is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0157] In equation (1-1), X 2 Preferably, it represents an organic group that contains a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of the following formulas (V-1) to (V-10).

[0158] Through X 2 Organic groups comprising structures obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-10) improve the chemical resistance and flatness of the cured product.

[0159] And, through X 2 Organic groups that contain structures obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-5) can also achieve effects such as suppressing the generation of developing residues, reducing the dielectric constant of the cured product, and decreasing the coefficient of thermal expansion.

[0160] By removing two or more hydrogen atoms from the organic groups of structures represented by any one of formulas (V-6) to (V-10), it is also possible to obtain effects such as increasing the transmittance of ultraviolet light, making the pattern of the cured material less likely to become conical, and having a wide tolerance for exposure.

[0161] Among these, from the viewpoint of reducing CTE, the structure represented by formula (V-4) or formula (V-5) is particularly preferred.

[0162] [Chemical Formula 14]

[0163]

[0164] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0165] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0166] In equation (V-8), R X5 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0167] In equation (V-2), R X1 Preferably, each component is an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0168] In equation (V-3), R X2 and R X3 Preferably, each hydrogen atom is an independent hydrogen atom.

[0169] In R X2 With R X3 In the case of bonding to form a ring structure, R X2 With R X3 The structure formed by bonding is preferably a single bond, -O- or -C(R)2-, more preferably -O- or -C(R)2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, alkyl or aryl, and even more preferably a hydrogen atom.

[0170] In equation (V-8), R X5 Preferably, each component is an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0171] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 2 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups, n1 represents an integer from 0 to 5, and is preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 3 Or, known substituents such as hydrocarbon groups.

[0172] [Chemical Formula 15]

[0173]

[0174] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), X2 Preferably, the group represented by formula (V-2-1) or formula (V-2-2) is preferred. From the viewpoint of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. In this specification, the bond that crosses the edge of the ring structure refers to the bond that replaces any one of the hydrogen atoms in the ring structure. In the following formula, L X1 The symbol represents a single bond or -O-, and * represents the X in equation (1-1). 2 The bonding sites of the four carbonyl groups. Furthermore, R X1 The definition and preferred method are as described above. Furthermore, the hydrogen atoms in these structures can be further converted by R in formula (1-1). 3 Or, known substituents such as hydrocarbon groups.

[0175] [Chemical Formula 16]

[0176]

[0177] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), X 2 Preferably, the group represented by formula (V-3-1) or formula (V-3-2) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-2) is preferred. In the following formulas, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups. Furthermore, R X2 and R X3 The definition and preferred method are as described above. Furthermore, the hydrogen atoms in these structures can be further converted by R in formula (1-1). 3 Or, known substituents such as hydrocarbon groups.

[0178] [Chemical Formula 17]

[0179]

[0180] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), X 2 Preferably, it is a group represented by the following formula (V-4-1).

[0181] In the following equation (V-4-1), * denotes X in equation (1-1). 2 The bonding sites of the four carbonyl groups are defined by n1, which represents an integer from 0 to 5. Furthermore, the hydrogen atom in formula (V-4-1) can be further bonded by R in formula (1-1). 3Alternatively, it may be substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, haloalkyl groups, and halogen atoms. Preferably, the hydrogen atoms in the structure represented by (V-4-1) are not substituted.

[0182] [Chemical Formula 18]

[0183]

[0184] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), X 2 Preferably, it is a group represented by the following formula (V-5-1). In the following formula, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atom in formula (V-5-1) can be further bonded by the R in formula (1-1). 3 Alternatively, it may be substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, haloalkyl groups, and halogen atoms. Preferably, the hydrogen atoms in the structure represented by (V-5-1) are not substituted.

[0185] [Chemical Formula 19]

[0186]

[0187] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), X 2 Preferably, it is a group represented by the following formula (V-6-1). In the following formula, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 3 Or, known substituents such as hydrocarbon groups.

[0188] [Chemical Formula 20]

[0189]

[0190] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), X 2 Preferably, it is a group represented by the following formula (V-7-1). In the following formula, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 3 Or, known substituents such as hydrocarbon groups.

[0191] [Chemical Formula 21]

[0192]

[0193] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), X 2 Preferably, it is a group represented by the following formula (V-8-1). In the following formula, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups. R X5 The definition and preferred method are as described above. Furthermore, the hydrogen atom in the following structure can be further reacted with R in formula (1-1). 3 Or, known substituents such as hydrocarbon groups.

[0194] [Chemical Formula 22]

[0195]

[0196] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), X 2 Preferably, it is a group represented by the following formula (V-9-1). In the following formula, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 3 Or, known substituents such as hydrocarbon groups.

[0197] [Chemical Formula 23]

[0198]

[0199] In X 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10), X 2 Preferably, it is a group represented by the following formula (V-10-1). In the following formula, * represents X in formula (1-1). 2 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 3 Substitution with known substituents such as hydrocarbon groups.

[0200] [Chemical Formula 24]

[0201]

[0202] In addition, X 2It can be the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic acid dianhydride as described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0203] And, X 2 Preferably, the structure does not contain imide bonds.

[0204] And, X 2 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0205] In this invention, the carbamate bond is *-OC(=O)-NR. N -* represents the key, R N Represents a hydrogen atom or a monovalent organic group, with * indicating the bonding site with a carbon atom. R N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.

[0206] In this invention, the urea bond is *-NR. N -C(=O)-NR N -* represents the key, R N Each symbol represents a hydrogen atom or a monovalent organic group independently, and * indicates the bonding site with a carbon atom. R N The preferred method is as described above.

[0207] In addition, X 2 Preferably, the structure does not contain ester bonds.

[0208] In this invention, the ester bond is represented by *-OC (=O)-*.

[0209] Among these, X 2 Preferably, it does not contain imide bonds, urethane bonds, urea bonds, and amide bonds; more preferably, it does not contain imide bonds, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0210] And, X 2 X can be the structure represented by the following equation (X-2) or X in the structure represented by (X-2). 2 The hydrogen atom or L in the group represented 3 The hydrogen atoms of the group represented are represented by R in formula (1-1). 3 The structure represented by the substituent group.

[0211] [Chemical Formula 25]

[0212]

[0213] In equation (X-2), X 2 Each of the three independent connective bases, L3 The symbol indicates a divalent linker, and * indicates a bonding site with other structures.

[0214] In equation (X-2), X 2 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, or groups obtained by linking two or more of these groups through single bonds or linking groups. Preferably, these are 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 obtained by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0215] As the linking group mentioned above, it is preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or a linking group obtained by bonding two or more of these, and more preferably -O-, -S-, alkylene, alkyl halide, arylene, or a linking group obtained by bonding two or more of these.

[0216] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0217] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but it is preferable that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0218] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0219] And, X 2 Preferably, the compound is derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. Chlorination is preferred as the halogenation method described above.

[0220] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0221] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-substituted.

[0222] Examples of tricarboxylic acid compounds that can be halogenated include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0223] These tricarboxylic acid compounds can be used in one or more forms.

[0224] X 2 Preferably, the structure does not contain an imide structure.

[0225] And, X 2 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0226] In addition, X 2 Preferably, the structure does not contain ester bonds.

[0227] Among these, X 2 Preferably, it does not contain an imide structure, a carbamate bond, a urea bond, or an amide bond; more preferably, it does not contain an imide structure, a carbamate bond, a urea bond, an amide bond, or an ester bond.

[0228] Specifically, the preferred tricarboxylic acid compound is a tricarboxylic acid compound containing 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 obtained by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a tricarboxylic acid compound obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through single bonds or linking groups.

[0229] Furthermore, specific examples of tricarboxylic acid compounds include compounds obtained by linking 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) with benzoic acid via single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene oxide.

[0230] These compounds can be compounds in which two carboxyl groups are anhydrinated (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride acyl chloride).

[0231] In equation (X-2), L 3Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, or groups obtained by linking two or more of these groups through single bonds or linking groups. Preferably, these are 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 obtained by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups obtained by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0232] As the linking group mentioned above, it is preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or a linking group obtained by bonding two or more of these, and more preferably -O-, -S-, alkylene, alkyl halide, arylene, or a linking group obtained by bonding two or more of these.

[0233] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0234] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but it is preferable that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0235] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0236] And, X 2 X can be the structure represented by the following equation (X-3) or X in the structure represented by (X-3). 2 The hydrogen atom or L in the group represented 3 The hydrogen atoms of the group represented are represented by R in formula (1-1). 3 The structure represented by the substituent group.

[0237] [Chemical Formula 26]

[0238]

[0239] In equation (X-3), X 2Each of the three independent connective bases, L 3 The symbol indicates a divalent linker, and * indicates a bonding site with other structures.

[0240] In equation (X-3), X 2 and L 3 The preferred method is the same as X in equation (X-2). 2 and L 3 The preferred method is the same.

[0241] -Y 2 -

[0242] Y 2 The carbon number is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0243] In equation (1-1), Y 2 It can be a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10).

[0244] The chemical resistance and flatness of the cured material are improved by removing two or more hydrogen atoms from the organic groups of the structure represented by any one of formulas (V-1) to (V-10).

[0245] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y 2 Preferably, it is a group represented by the following formula (V-1-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms, n1 represents an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in equation (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0246] [Chemical Formula 27]

[0247]

[0248] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y 2 Preferably, the group represented by formula (V-2-3) or formula (V-2-4) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-2-4) is preferred. In the following formula, L X1 * indicates a single bond or -O-, and * indicates a Y in equation (1-1) 2 The bonding sites of the two nitrogen atoms. Furthermore, RX1 The preferred method is as described above. Furthermore, the hydrogen atoms in these structures can be further converted by R in formula (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0249] [Chemical Formula 28]

[0250]

[0251] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y 2 Preferably, the group represented by formula (V-3-3) or formula (V-3-4) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-3) is preferred. In the following formulas, * represents Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in these structures can be further bonded by R in formula (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0252] [Chemical Formula 29]

[0253]

[0254] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y 2 Preferably, it is a group represented by the following formula (V-4-2) or (V-4-3). In the following formulas, * represents the group corresponding to Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms are denoted by n1, which is an integer from 0 to 5. Furthermore, n1 being 0 is also one of the preferred embodiments of the present invention. Additionally, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 4 Alternatively, it may be replaced by known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, haloalkyl groups, and halogen atoms.

[0255] [Chemical Formula 30]

[0256]

[0257] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), Y 2 Preferably, it is a group represented by the following formula (V-5-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 2The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atom in formula (V-5-2) can be further bonded by R in formula (1-1). 4 Alternatively, it may be substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, haloalkyl groups, and halogen atoms. Preferably, the hydrogen atoms in the structure represented by (V-5-1) are not substituted.

[0258] [Chemical Formula 31]

[0259]

[0260] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), Y 2 Preferably, it is a group represented by the following formula (V-6-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0261] [Chemical Formula 32]

[0262]

[0263] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), Y 2 Preferably, it is a group represented by the following formula (V-7-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0264] [Chemical Formula 33]

[0265]

[0266] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), Y 2 Preferably, it is a group represented by the following formula (V-8-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0267] [Chemical Formula 34]

[0268]

[0269] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), Y 2 Preferably, it is a group represented by the following formula (V-9-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0270] [Chemical Formula 35]

[0271]

[0272] In Y 2 In the case of a base containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10), Y 2 Preferably, it is a group represented by the following formula (V-10-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 2 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further bonded by R in formula (1-1). 4 Or, known substituents such as hydrocarbon groups.

[0273] [Chemical Formula 36]

[0274]

[0275] In addition, Y 2 It can be the basis recorded in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421.

[0276] Furthermore, Y 2 Preferably, the structure does not contain imide bonds.

[0277] Furthermore, Y 2 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0278] In addition, Y 2 Preferably, the structure does not contain ester bonds.

[0279] Among these, Y 2 Preferably, it does not contain imide bonds, urethane bonds, urea bonds, and amide bonds; more preferably, it does not contain imide bonds, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0280] Among these, X in the preferred formula (1-1) 2 and Y 2 All of them contain a ring structure, more preferably they contain an organic group that is obtained by removing two or more hydrogen atoms from the structure represented by any one of the above formulas (V-1) to (V-10), and even more preferably they contain an organic group that is obtained by removing two or more hydrogen atoms from the structure represented by any one of the above formulas (V-1) to (V-5). The preferred manner of these groups is as described above.

[0281] -n and m-

[0282] In formula (1-1), m is preferably an integer from 0 to 2, more preferably 0 or 1. Furthermore, m being 0 is also one of the preferred embodiments of the present invention.

[0283] In formula (1-1), n ​​is preferably 1 or 2, and more preferably 2.

[0284] -R 3 and R 4 -

[0285] R 3 and R 4 Each of the following equations (R-1) can be used to represent the structure independently.

[0286] [Chemical Formula 37]

[0287]

[0288] In equation (R-1), L 1 A represents a linker base with valence a1+1. 1 This represents the structure indicated by equation (P-1) or (P-2) above, where a1 represents an integer greater than or equal to 1, and * represents the structure related to X in equation (1-1). 2 Or Y 2 The bonding sites.

[0289] In equation (R-1), L 1 Preferably, it is a group represented by the following formula (L-1).

[0290] [Chemical Formula 38]

[0291]

[0292] In equation (L-1), Z 1 Indicates -O-, -NR N -, -C(=O)O-or-C(=O)NR N -, R N L represents a hydrogen atom or a monovalent organic group, where a1 is 1. xL represents a single bond or a divalent linker, where a1 is 2 or more. x This represents a linker basis with valence a1+1, where a1 represents an integer greater than or equal to 1, and * denotes the connection with X in equation (1-1). 2 Or Y 2 The bonding site, # indicates the bonding with A in equation (R-1). 1 The bonding sites.

[0293] In equation (L-1), Z 1 Preferably -O- or -C(=O)O-. Furthermore, in Z... 1 For -NR N In the case of -R N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and even more preferably a hydrogen atom.

[0294] In equation (L-1), when a1 is 1, L x Preferably, it is an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and especially preferably a methylene group.

[0295] In equation (L-1), when a1 is 2 or more, L x Preferably, it is a hydrocarbon group, a heterocyclic group, or a group represented by a combination of these groups, more preferably a saturated aliphatic hydrocarbon group with 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group with 3 to 15 carbon atoms.

[0296] In equation (L-1), a1 has the same meaning as a1 in equation (R-1).

[0297] In equation (R-1), A 1 The preferred configuration of the structure represented by formula (P-1) or formula (P-2) is as described above.

[0298] Among these, A in the preferred formula (R-1) 1 The structure represented by equation (P-1) and L 1 It is the group represented by formula (L-2-1).

[0299] [Chemical Formula 39]

[0300]

[0301] In equation (L-2-1), L X2 'a1' represents a hydrocarbon group, and 'a1' represents an integer greater than or equal to 1.

[0302] In equation (L-2-1), L X2 It represents a hydrocarbon group, preferably an aliphatic saturated hydrocarbon group.

[0303] When a1 is 1, L X2 Preferably, it is an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and especially preferably a methylene group.

[0304] In equation (L-2-1), a1 has the same meaning as a1 in equation (R-1).

[0305] Furthermore, A in the preferred formula (R-1) 1 The structure represented by equation (P-2), L 1 The group represented by formula (L-1) and L X It is an aromatic group or an aliphatic saturated hydrocarbon group with 4 or more carbon atoms.

[0306] The aromatic group can be any one of an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group.

[0307] As an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group with 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group with 6 carbon atoms.

[0308] Examples of heteroatoms in aromatic heterocyclic groups include oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the aromatic heterocyclic group is preferably one or two. Furthermore, the aromatic heterocyclic group is preferably a 5-membered or 6-membered ring containing the aforementioned heteroatoms. Additionally, other aromatic heterocyclic groups or other aromatic hydrocarbon cyclic groups may be condensed within the aromatic heterocyclic group.

[0309] As an aliphatic saturated hydrocarbon group with 4 or more carbon atoms, it can be any of the following structures: straight-chain, branched-chain, cyclic, or a combination thereof.

[0310] The aliphatic saturated hydrocarbon group with 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms.

[0311] In formula (R-1), a1 is preferably an integer from 1 to 4, and more preferably an integer from 1 to 2. Furthermore, a1 being 1 is also one of the preferred embodiments of the present invention.

[0312] Furthermore, from the viewpoint of reducing the dielectric loss tangent, the number of ester groups contained in formula (R-1) is preferably 1 or 0.

[0313] [The structure represented by equation (2-1) or equation (2-2)]

[0314] Polyamic acid preferably comprises the structure represented by formula (2-1) or formula (2-2) below.

[0315] Here, the resin composition is preferably a resin containing a structure represented by the following formula (2-1) and a resin containing a structure represented by the following formula (2-2).

[0316] Furthermore, the resin composition is preferably a resin containing the structure represented by the following formula (2-1) and compound C described later.

[0317] In addition, the resin composition is preferably a resin containing the structure represented by the following formula (2-2) and compound B described later.

[0318] [Chemical Formula 40]

[0319]

[0320] In equations (2-1) and (2-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 Each independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, V 1 Z represents a linker base that is either a single bond or divalent. 1 Q represents the amino group that can be protected. 1 R represents a structure containing a protected carboxyl group. 3 R 4 Each of the above formulas (R-1) can be used to represent the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

[0321] In equations (2-1) and (2-2), X 2 Y 2 R 1 R 2 R 3 R 4 The preferred methods for m and n are the same as those for X in equation (1-1). 2 Y 2 R 1 R 2 R 3 R 4 The preferred methods for m and n are the same.

[0322] -V 1 -

[0323] In equation (2-1), V 1 Preferably, it is a group represented by the following formula (V1-1).

[0324] [Chemical Formula 41]

[0325]

[0326] In equation (V1-1), V 2 The symbol represents a divalent linker, * indicates a bonding site with the carbonyl group in formula (2-1), and # indicates a bonding site with the Z group. 1 The bonding sites.

[0327] V 2 The preferred method is the same as Y in the above formula (1-1). 2 The preferred method is the same.

[0328] -Z 1 -

[0329] Z 1 This indicates an amino group that can be protected.

[0330] The protected amino group can be either an unsubstituted amino group (-NH2) or a protected amino group (-N(R)2, where R represents a hydrogen atom or an organic group, and at least one of the two Rs is an organic group. Furthermore, R is preferably a hydrocarbon group.)

[0331] The protected amino group is preferably a group that generates an amino group through light, heat, acid or alkali.

[0332] The amino group derived from the protected amino group is preferably an unsubstituted amino group (-NH2).

[0333] The following methods can be used to confirm whether the protected amino group is a group that generates amino groups through light.

[0334] For a 1% N-methylpyrrolidone solution of a specific resin, under conditions of 1 atmosphere pressure and 25°C, light with wavelengths of 190–800 nm was emitted at 25 W / cm². 2 After being exposed to the specified illuminance for 60 seconds, through... 1 Methods such as H-NMR can be used to confirm whether amino groups have been generated.

[0335] When the protected amino group is a group that generates an amino group by heat, it is preferred to generate an amino group by heat at 180°C, more preferably by heat at 200°C, and even more preferably by heat at 230°C.

[0336] The heating time for producing alkali is preferably 180 minutes, more preferably 120 minutes, and even more preferably 60 minutes.

[0337] The following method can be used to confirm whether the protected amino group is a group that produces an amino group by heating at a certain temperature X℃ for a certain time Y hours.

[0338] A 1% (w / w) N-methylpyrrolidone solution of a specific resin was exposed to heating at X °C for Y hours, and then... 1 Methods such as H-NMR can be used to confirm whether amino groups have been generated.

[0339] The following methods can be used to confirm whether the protected amino group is a group that generates an amino group through an acid.

[0340] To a 1% by mass N-methylpyrrolidone solution of a specific resin, 1% by mass methanesulfonic acid relative to the solid content of the resin was added, and the solution was allowed to stand at 25°C for 60 minutes. Then, the solution was analyzed by... 1 Methods such as H-NMR can be used to confirm whether amino groups have been generated.

[0341] The following methods can be used to confirm whether the protected amino group is a group that generates an amino group through a base.

[0342] To a 1% by mass N-methylpyrrolidone solution of a specific resin, a 10% by mass methanol solution of tetrabutylammonium hydroxide (relative to 1% by mass of the resin solids) was added, and the mixture was allowed to stand at 25°C for 60 minutes. Then, the solution was... 1 Methods such as H-NMR can be used to confirm whether amino groups have been generated.

[0343] Among these, Z 1 Preferably, it represents the organic group represented by the following formula (AM-1).

[0344] [Chemical Formula 42]

[0345]

[0346] In formula (AM-1), Q 1 The symbol represents a hydrogen atom or a group represented by the following formula (AM-2), and * represents the group corresponding to V in formula (2-1). 1 The bonding sites.

[0347] [Chemical Formula 43]

[0348]

[0349] In formula (AM-2), T 1 The symbol represents a monovalent organic group, and * indicates the bonding site with the nitrogen atom in formula (2-1).

[0350] In formula (AM-2), T 1 Preferably, it is an alkyl group or an alkyl group substituted with a cyclic structure, more preferably a tertiary alkyl group or a methyl group substituted with a cyclic structure, and even more preferably a tert-butyl group or a 9-fluorenylmethyl group.

[0351] -Q 1 -

[0352] Q1 This indicates a carboxyl group that can be protected.

[0353] The carboxyl group that can be protected can be either an unsubstituted carboxyl group (-COOH) or a protected carboxyl group (-COO(R), where R represents an organic group, preferably a hydrocarbon group).

[0354] Q 1 Preferably, the structure has two or more carboxyl groups that can be protected, linked by linkers with a chain length of 2 to 4 (also known as "structure A").

[0355] Here, the linking chain length in structure A refers to the minimum number of atoms contained in structure A and existing between the carbonyl groups in each of the two groups selected from the carboxylic acid ester group and the protected carboxyl group contained in structure A.

[0356] And Q 1 The carboxyl group in the composition can be a carboxylic acid ester group. The carboxylic acid ester group is -C(=O)O. - The group represented. There is no particular limitation on the counter cation relative to the anionic portion mentioned above; examples include protons and Na+. + K + Metal cations, ammonium cations, imine cations, etc.

[0357] The protected carboxyl group is preferably a group that generates an amino group through light, heat, acid or alkali.

[0358] The protected carboxyl group is preferably alkoxycarbonyl or aryloxycarbonyl, and more preferably tert-butyloxycarbonyl.

[0359] Furthermore, the protected carboxyl group is preferably a group that generates a carboxyl group through light, heat, acid or alkali.

[0360] Whether a group generates a carboxyl group through light, heat, acid, or alkali can be determined using the same method as described above for determining whether a group generates an amino group. In this method, the part described as amino in the above determination method will be replaced with a carboxyl group.

[0361] In equation (2-2), Q 1 Preferably, a structure comprising any one of the following formulas (S-1) to (S-4) is used as a structure containing a protected carboxyl group. These structures are structures containing structure A.

[0362] [Chemical Formula 44]

[0363]

[0364] In equations (S-1) to (S-4), RS1 Represents -OH, -O - or -OR S2 R S2 Indicates a protecting group, Cy indicates an aliphatic ring structure, and L represents a protecting group. 1 This indicates an aliphatic base with a single bond or linker chain length of 1 or 2, where n represents an integer of 1 or 2, and * indicates a bonding site with other structures.

[0365] In equations (S-1) to (S-4), R S1 Preferably -OH or -O - R S1 -O - There are no particular limitations on the counter cations at any given time; examples include protons and Na+. + K + Metal cations, ammonium cations, imine cations, etc.

[0366] In R S1 Indicates -OR S2 In the case of R S2 Preferably alkyl or aryl, more preferably alkyl with 1 to 4 carbon atoms, and even more preferably tert-butyl.

[0367] Cy is preferably a cycloalkane structure, and more preferably a cyclohexane ring structure.

[0368] n is preferably 1.

[0369] L 1 Preferably, it is a single bond, methylene, or ethylene, and more preferably a single bond.

[0370] In equation (2-2), Q 1 Preferably, it is a group represented by the following formula (Q1-1).

[0371] [Chemical Formula 45]

[0372]

[0373] In equation (Q1-1), X 2 R represents an organic group with 4 or more carbon atoms. 1 R represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 3 This represents the structure indicated by the above formula (R-1), where m represents an integer from 0 to 4, and # represents the relationship between Q and 0. 1 The bonding sites.

[0374] In equation (Q1-1), X 2 R 1 R 2 R 3 The preferred method for m is the same as X in equation (1-1). 2 R1 R 2 R 3 The preferred method for m is the same.

[0375] In equation (Q1-1), R Q1 and R Q2 The preferred method is the same as R in the above formula (S-1). S1 The preferred method is the same.

[0376] In formula (Q1-1), it is preferred to use X 2 or X 2 Part of, containing R Q1 Structure and inclusion of R Q2 The structure can be formed to represent any one of the above formulas (S-1) to (S-4), and more preferably to represent the structure represented by the above formula (S-1) or (S-3).

[0377] [The repeating unit represented by equation (4-1)]

[0378] A particular resin may contain repeating units represented by formula (4-1). The repeating units represented by formula (4-1) are repeating units that do not contain the structures represented by formula (P-1) and formula (P-2) and do not correspond to the repeating units represented by formula (1-1).

[0379] [Chemical Formula 46]

[0380]

[0381] In equation (4-1), X 4 Y represents an organic group with 4 or more carbon atoms. 4 R represents an organic group with 4 or more carbon atoms. 41 and R 42 Each can be independently represented by an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0382] In equation (4-1), X 4 Y 4 R 41 and R 42 The preferred method is the same as X in equation (1-1) 2 Y 2 R 1 and R 2 The preferred method is the same.

[0383] [The repeating unit represented by equation (3-1)]

[0384] A particular resin may contain repeating units represented by formula (3-1).

[0385] [Chemical Formula 47]

[0386]

[0387] In equation (3-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of the following expressions (R-2) can be used to independently represent the structure represented by m, where m represents an integer from 0 to 4 and n represents an integer greater than or equal to 1.

[0388] [Chemical Formula 48]

[0389]

[0390] In equation (R-2), L 2 A represents a linker basis with a valence of a²+1. 2 The symbol represents a polymerizable group, a2 represents an integer greater than or equal to 1, and * represents X in equation (3-1). 1 Or Y 1 The bonding sites.

[0391] In equation (3-1), X 1 Y 1 The preferred methods for m and n are the same as those for X in equation (1-1). 2 Y 2 The preferred methods for m and n are the same.

[0392] In equation (R-2), A is... 2 The polymerizable groups in it are preferably groups having olefinic unsaturated bonds.

[0393] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0394] Among these, (meth)acryloyl, (meth)acrylamido, vinylphenyl, or maleimide are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity. Furthermore, vinylphenyl or maleimide is preferred from the viewpoint of reducing dielectric loss tangent.

[0395] Among these, A 2 Preferably, the group is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, or a group containing these, more preferably maleimide, (meth)acryloyloxy, (meth)acrylamido, or vinylphenyl. In particular, from the viewpoint of reactivity, (meth)acryloyloxy is preferred. Furthermore, from the viewpoint of reducing the dielectric loss tangent of the cured product, maleimide or vinylphenyl is preferred.

[0396] In particular, A in formula (R-2) included in formula (3-1) is preferred. 2 At least one of them is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl, epoxy or a group containing these, more preferably maleimide, (meth)acryloyloxy, (meth)acrylamido or vinylphenyl, more preferably vinylphenyl.

[0397] In equation (R-2), L 2 The preferred method for a2 is the same as L in the above formula (R-1). 1 The preferred method is the same as that for a1.

[0398] [The repeating unit represented by equation (5-1)]

[0399] A particular resin may contain repeating units represented by formula (5-1). The repeating unit represented by formula (5-1) is a repeating unit that does not contain the structure represented by formula (R-1) and does not correspond to the repeating unit represented by formula (3-1).

[0400] [Chemical Formula 49]

[0401]

[0402] In equation (5-1), X 5 Y represents an organic group with 4 or more carbon atoms. 5 This refers to an organic group that has 4 or more carbon atoms.

[0403] In equation (5-1), X 5 and Y 5 The preferred method is the same as X in equation (4-1) 4 and Y 4 The preferred method is the same.

[0404] The content of the repeating unit represented by formula (1-1) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, relative to the total mass of the specific resin. There is no particular limitation on the upper limit of the above content, and it can be 100% by mass.

[0405] The total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (4-1) relative to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. There is no particular limitation on the upper limit of the above content, and it can be 100% by mass.

[0406] Furthermore, the total content of the repeating units represented by formula (1-1), formula (4-1), formula (3-1), and formula (5-1) relative to the total mass of the specific resin 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. There is no particular upper limit to the above content, and it can be 100% by mass.

[0407] In these methods, a particular resin may contain two or more repeating units represented by formula (1-1) with different structures. In this case, the total amount is preferably within the range described above.

[0408] In these methods, a particular resin may contain two or more repeating units represented by formula (4-1) with different structures. In this case, the total amount is preferably within the range described above.

[0409] In the case where a particular resin contains repeating units represented by formula (3-1), it may contain two or more repeating units represented by formula (3-1) with different structures. In this case, it is preferable that the total amount is within the above range.

[0410] In the case where a particular resin contains repeating units represented by formula (5-1), it may contain two or more repeating units represented by formula (5-1) with different structures. In this case, it is preferable that the total amount is within the above range.

[0411] The weight-average molecular weight (Mw) of a particular resin is preferably 3,000 to 100,000.

[0412] The lower limit of Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.

[0413] The upper limit of Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0414] By setting the weight-average molecular weight to 3,000 or higher, the folding resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 5,000 or higher is particularly preferred.

[0415] The number-average molecular weight (Mn) of the specific resin is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0416] The molecular weight dispersion of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular limitation on the upper limit of the molecular weight dispersion of the specific resin, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0417] In this specification, the molecular weight dispersion is a value calculated based on the weight-average molecular weight / number-average molecular weight.

[0418] When the resin composition comprises multiple specific resins as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple resins are considered as one resin are each within the above-mentioned ranges.

[0419] The imidization rate (also known as "ring-closing rate") of a particular resin is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. There is no particular limitation on the lower limit of the imidization rate mentioned above, as long as it is 0% or more.

[0420] The imidization rate described above can be determined, for example, by the following method.

[0421] The infrared absorption spectrum of a specific resin was measured, and the absorption peak at 1377 cm⁻¹, which is derived from the imide structure, was determined. -1 The peak intensity P1 is located nearby. Next, after heat-treating the specific resin at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity at 1377 cm⁻¹ was determined. -1 The peak intensity P2 is nearby. The obtained peak intensities P1 and P2 can be used to determine the imidization rate of a specific resin according to the following formula.

[0422] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0423] [Manufacturing method of specific resins]

[0424] Specific resins can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine at low temperature; by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid and then alkylating it with a condensing agent or alkylating agent as needed; by obtaining diesters with tetracarboxylic dianhydride or the aforementioned dianhydride and alcohol, and then reacting them in the presence of diamine and a condensing agent; by obtaining diesters with tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acids with a halogenating agent and reacting them with diamine, etc.

[0425] Examples of condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0426] 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.

[0427] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0428] In methods for manufacturing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types.

[0429] As an organic solvent, it can be appropriately set according to the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0430] In methods for manufacturing polyimide precursors, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.

[0431] The basic compound can be appropriately set according to the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0432] -End- Capping Agent-

[0433] In the manufacturing method of a specific resin, to further improve storage stability, it is preferable to seal the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of the specific resin. When sealing the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monools, phenols, thiols, thiophenols, and monoamines. From the viewpoint of reactivity and film stability, monools, phenols, or 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, tert-butyl alcohol, 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-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. Examples of amino acids include 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, and 4-aminobenzenethiophenol. More than two of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0434] Furthermore, when sealing the amino group at the end of the resin, a compound having a functional group capable of reacting with the amino group can be used for sealing. Preferred sealants for the amino group 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. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of preferred carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, and benzoyl chloride.

[0435] In addition, by bonding a terminal seal with a protected amino group to the end of the resin, it is also possible to introduce a protected amino group into the resin.

[0436] Specifically, the structure represented by the above formula (2-1) can be introduced into the resin by reacting the compound represented by the following formula (T-1) with a resin whose terminal component is a carboxylic acid (or carboxylic anhydride).

[0437] [Chemical Formula 50]

[0438]

[0439] In equation (T-1), V 1 Z represents a linker base that is either a single bond or divalent. 1 This indicates an amino group that can be protected.

[0440] In equation (T-1), V 1 and Z 1 The preferred method is the same as V in equation (2-1) 1 and Z 1 The preferred method is the same.

[0441] Furthermore, by bonding a terminal seal with a protected carboxyl group to the end of the resin, it is also possible to introduce a protected carboxyl group into the resin.

[0442] -Solid precipitation-

[0443] The manufacturing method of a specific resin may include a step of precipitating a solid. 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, causing the polymer component to precipitate as a solid and then dry it, thereby obtaining the specific resin. To improve the purification degree, the specific resin may be repeatedly subjected to operations such as re-dissolving, re-precipitating, and drying. Furthermore, the method may include a step of using an ion exchange resin to remove ionic impurities.

[0444] 〔content〕

[0445] The content of a specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, even more preferably 50% by mass or more, and most preferably 60% by mass or more, relative to the total solids content of the resin composition. Furthermore, the content of the specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and still more preferably 95% by mass or less, relative to the total solids content of the resin composition.

[0446] <Other Resins>

[0447] The resin composition of the present invention may contain other resins (hereinafter also referred to as "other resins") that are different from the specific resins described above.

[0448] Other resins include resins that are different from a specific resin, and resins that correspond to polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamide-imide precursors, polyamide-imides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, etc.

[0449] As other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamide-imide precursors, and polyamide-imides, examples include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above descriptions are incorporated herein by reference.

[0450] [Resin B]

[0451] From the viewpoint of suppressing curing shrinkage, the resin composition of the present invention preferably further comprises a resin (also referred to as "resin B") that is different from a particular resin and contains repeating units represented by the above formula (3-1).

[0452] Resin B is preferably polyimide.

[0453] Resin B may further include the repeating unit represented by formula (5-1).

[0454] Furthermore, the total content of the repeating unit represented by formula (3-1) and the repeating unit represented by formula (5-1) relative to the total mass of resin B 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. There is no particular limitation on the upper limit of the above content, and it can be 100% by mass.

[0455] When resin B contains the repeating unit represented by formula (3-1), it may contain two or more repeating units represented by formula (3-1) with different structures. In this case, it is preferable that the total amount is within the above range.

[0456] When resin B contains the repeating unit represented by formula (5-1), it may contain two or more repeating units represented by formula (5-1) with different structures. In this case, it is preferable that the total amount is within the above range.

[0457] When the resin composition contains resin B, from the viewpoint of reducing the coefficient of thermal expansion, the ratio of the content of resin B to the total content of the specific resin and resin B is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass.

[0458] The weight-average molecular weight (Mw) of resin B is preferably 3,000 to 100,000.

[0459] The lower limit of Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.

[0460] The upper limit of Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0461] By setting the weight-average molecular weight to 3,000 or higher, the folding resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 5,000 or higher is particularly preferred.

[0462] The number average molecular weight (Mn) of resin B is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0463] The molecular weight dispersion of resin B is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular limitation on the upper limit of the molecular weight dispersion of resin B; for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, and even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0464] When the resin composition comprises multiple resins as resin B, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple resins are considered as one resin are each within the above-mentioned ranges.

[0465] From the viewpoint of suppressing curing shrinkage, the imidization rate of resin B is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular limitation on the lower limit of the above imidization rate; it is acceptable as long as it is 0% or more.

[0466] 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.

[0467] 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.

[0468] As a preferred embodiment of the resin composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins 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 still more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0469] 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.

[0470] <Compounds with protected amino groups (Compound B)>

[0471] The resin composition of the present invention comprises a compound having two or more protected amino groups and a molecular weight of less than 2,000 (also referred to as "compound B").

[0472] The preferred manner in which the protected amino group is located is the same as that in the specific resin described above.

[0473] The above-mentioned compound B preferably has an aromatic group.

[0474] Furthermore, the amino group in compound B, or the amino group derived from the protected amino group, is preferably an aromatic amino group.

[0475] In this invention, aromatic amino refers to a structure in which the aromatic ring and amino group are bonded by a single bond without a linker.

[0476] The aromatic group in compound B can be any of an aromatic hydrocarbon group or a heteroaromatic cyclic group, but is preferably an aromatic hydrocarbon cyclic group or a heteroaromatic cyclic group containing a nitrogen atom as a cyclic atom, and more preferably an aromatic hydrocarbon group.

[0477] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group is preferably an aromatic hydrocarbon ring with 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring with 6 to 10 carbon atoms, and even more preferably a benzene ring.

[0478] Examples of heteroaromatic rings in heteroaromatic ring groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, imidazole rings, triazole rings, tetraazole rings, oxazole rings, pyridine rings, pyridazine rings, pyrazine rings, triazine rings, indole rings, indazole rings, benzimidazole rings, and purine rings.

[0479] Examples of aliphatic rings in cyclic aliphatic groups include aliphatic hydrocarbon rings with 5 to 20 carbon atoms, pyrrolidine rings, pyrrololine rings, pyrazolidine rings, imidazoidine rings, piperidine rings, piperazine rings, tetrahydropyran rings, dioxane rings, and morpholine rings.

[0480] Furthermore, compound B preferably has a liquid crystal protoframe.

[0481] In this specification, the liquid crystal proto-framework refers to a structure containing a polycyclic aromatic hydrocarbon or two or more aromatic rings, preferably a structure with rigidity and orientation.

[0482] Regarding compound B, as the original framework of the liquid crystal, it is preferably a structure in which two or more aromatic rings are connected by single bonds, -O-, -C(=O)O- or -NHC(=O)-.

[0483] As the aromatic ring, it is preferably the aromatic ring described above as an aromatic group, and more preferably a benzene ring.

[0484] The following are examples of preferred liquid crystal protoframes, but the invention is not limited to these. In the following structures, * indicates bonding sites with other structures.

[0485] [Chemical Formula 51]

[0486]

[0487] Compound B is preferably the compound represented by the following formula (B-1).

[0488] [Chemical Formula 52]

[0489]

[0490] In formula (B-1), L B1 Q represents an n-valent organic group. 1 The symbol represents a hydrogen atom or a group represented by the above formula (2-2), where n represents an integer greater than 2.

[0491] In formula (B-1), L B1Preferably, it is a hydrocarbon group, a heterocyclic group, or these groups combined with a group selected from -O-, -C(=O)-, -S-, -S(=O)2-, and -NR. N - A base obtained by bonding at least one type of base from the group. R N The preferred method is as described above.

[0492] Examples of the aforementioned hydrocarbon groups include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by the bonds of these groups.

[0493] Among these, L B1 Preferably, it contains a cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group. As a cyclic aliphatic hydrocarbon group, it is preferably a cyclic aliphatic hydrocarbon group with 5 to 20 carbon atoms, more preferably a cyclohexane ring. Furthermore, the preferred method for the aromatic hydrocarbon group is the same as the preferred method for the aromatic group in compound B described above.

[0494] Here, L B1 It is also preferred to use the group represented by formula (LB-1).

[0495] [Chemical Formula 53]

[0496]

[0497] In equation (LB-1), L B2 The symbol represents an n-valent organic group, Cy represents a ring structure, n represents the same number as n in formula (B-1), and * represents the bonding site with the nitrogen atom in formula (B-1).

[0498] In equation (LB-1), L B2 Preferably, it is an aromatic hydrocarbon group, an aliphatic hydrocarbon cyclic group, or these groups combined with a compound selected from -O-, -C(=O)-, -S-, -S(=O)2-, and -NR. N - A base obtained by bonding at least one base from the group.

[0499] In formula (LB-1), Cy is preferably an aromatic ring structure or an aliphatic hydrocarbon ring structure, more preferably an aromatic hydrocarbon ring structure, and even more preferably a benzene ring structure.

[0500] The following records L B1 This is a preferred embodiment, but the invention is not limited thereto. In the following structures, * indicates the bonding site with the nitrogen atom in formula (B-1).

[0501] [Chemical Formula 54]

[0502]

[0503] In equation (B-1), Q 1 The preferred manner of the group represented by formula (2-2) is the same as that of Q in formula (2-1) above.1 The preferred method is the same as that for the groups represented by formula (2-2).

[0504] In formula (B-1), n ​​is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, even more preferably 2 or 3, and especially preferably 2.

[0505] The molecular weight of compound B is preferably 230 to 1,500, more preferably 300 to 1,000.

[0506] The number of protected amino groups in compound B is preferably two or more, more preferably two to four, and even more preferably two.

[0507] The content of the protected amino group in 1g of compound B is preferably 1 to 10 mmol / g, more preferably 2 to 8 mmol / g, and even more preferably 3 to 6 mmol / g.

[0508] The content of compound B is preferably 0.1 to 10% by mass relative to the total solids content of the resin composition, more preferably 0.5 to 5% by mass.

[0509] <Compounds with structure A (Compound C)>

[0510] The resin composition of the present invention may contain compound C having two or more of the above-described structures A and having a molecular weight of 2,000 or less.

[0511] The preferred embodiment of structure A in compound C is the same as the preferred embodiment of structure A in the specific resin described above.

[0512] The compound C is preferably a compound represented by the following formula (C-1).

[0513] [Chemical Formula 55]

[0514]

[0515] In equation (C-1), X 3 J represents a tetravalent organic group. 1 and J 2 -O- or -NR can be represented independently. N -, R N R represents a hydrogen atom or a hydrocarbon group. 3 and R 4 Each of the above independently represents a monovalent organic group, G + They can be used to represent hydrogen cations or ammonium cations independently.

[0516] In equation (C-1), X 3 The preferred method is the same as X in the above formula (1-1). 2 The preferred method is the same.

[0517] In equation (C-1), J 1 and J 2 Ideally, they should be -O-, each independently.

[0518] In equation (C-1), in J 1 and J 2 At least one of them is -NR N In the case of -R N Hydrogen atoms are preferred.

[0519] In equation (C-1), R 3 and R 4 Preferably, each component is a hydrocarbon group, and more preferably an alkyl group.

[0520] The molecular weight of compound C is preferably 230 to 1,500, more preferably 300 to 1,000.

[0521] The number of structures A in compound C is preferably two or more, more preferably two to four, and even more preferably two.

[0522] The content of structure A in 1g of compound C is preferably 1 to 10 mmol / g, more preferably 1.5 to 9.0 mmol / g, and even more preferably 2.0 to 7.0 mmol / g.

[0523] The content of compound C is preferably 0.1 to 10% by mass relative to the total solids content of the resin composition, more preferably 0.5 to 5% by mass.

[0524] <Polymerizing compounds>

[0525] The resin composition of the present invention preferably contains a polymerizable compound.

[0526] The melting point of the polymerizable compound is preferably below 25°C.

[0527] By setting the melting point below 25°C, the coating film flows easily during drying and heating, which improves the flatness of the cured product.

[0528] Examples of polymerizable compounds include polymerizable compounds with free radical polymerizable groups (free radical crosslinking agents) or other crosslinking agents.

[0529] [Free radical cross-linking agent]

[0530] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0531] A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferably, the free radical polymerizable group is a group containing an olefinic unsaturated bond. Examples of such groups containing an olefinic unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0532] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0533] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, but more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may also have three or more olefinic unsaturated bonds.

[0534] The compounds having two or more olefinic unsaturated bonds are preferably compounds having 2 to 15 olefinic unsaturated bonds, more preferably compounds having 2 to 10 olefinic unsaturated bonds, and even more preferably compounds having 2 to 6 olefinic unsaturated bonds.

[0535] From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably includes compounds having two olefinic unsaturated bonds and the above-mentioned compounds having three or more olefinic unsaturated bonds.

[0536] 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.

[0537] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters or amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, it is also preferable to use addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids. Furthermore, 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 preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds that replace the aforementioned unsaturated carboxylic acids can also be used, such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers. 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.

[0538] The free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at atmospheric pressure. Examples of compounds having a boiling point of 100°C or higher at atmospheric pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0539] Other preferred free radical crosslinking agents besides those mentioned above include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

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

[0541] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups; SR-209, 231, and 239, difunctional methacrylates with four ethoxy groups (all manufactured by Sartomer Company, Inc.); DPCA-60, a hexafunctional acrylate with six pentyli groups; TPA-330, a trifunctional acrylate with three isobutylene groups (all manufactured by Nippon Kayaku Co., Ltd.); UAS-10 and UAB-140, urethane oligomers (all manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical). (Manufactured by Nippon Kayaku Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0542] As a free radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, or urethane compounds having an ethylene oxide backbone as described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418, are also preferred. 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 a free radical crosslinking agent.

[0543] The free radical crosslinking agent can also be a free radical crosslinking agent with acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent with acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is that, in the free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl tetrol or dinepentyl tetrol. Examples of commercially available products include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO.,LTD., such as M-510 and M-520.

[0544] The acid value of the free radical crosslinking agent containing acid groups is preferably 0.1 to 300 mg KOH / g, more preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and developability. Furthermore, it demonstrates good polymerizability. The acid value is determined according to the description in JIS K 0070:1992.

[0545] As a free radical crosslinking agent with an isocyanuric ring structure, it is preferably a compound having 2 or 3 free radical polymerizable groups, more preferably a compound having 3.

[0546] Furthermore, examples of free radical crosslinking agents having an isocyanuric ring structure include tris(2-acryloyloxyethyl) isocyanurate, tris(2-methacryloyloxyethyl) isocyanurate, EO (ethylene oxide) modified diacrylate, EO isocyanurate modified triacrylate, and compounds with the structures described below, but are not limited to these. In the structures described below, n independently represents an integer from 1 to 20, and R represents a divalent linker.

[0547] [Chemical Formula 56]

[0548]

[0549] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylates or acrylates.

[0550] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, and 3-methyl-1,5-pentanediol diacrylate can be used. Acid esters, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethyloltricyclodecane diacrylate, dimethyloltricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, difunctional acrylates having other urethane bonds, and difunctional methacrylates having urethane bonds. Two or more of these can be mixed as needed.

[0551] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain weight of approximately 200.

[0552] From the viewpoint of suppressing warping of the 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, preferably used are 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 other N-vinyl compounds, allyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at ambient pressure are also preferred.

[0553] In addition, examples of allyl compounds, such as diallyl phthalate and trimellitic acid, can be cited as free radical crosslinking agents with two or more functions.

[0554] When a free radical crosslinking agent is included, the content of the free radical crosslinking agent relative to the total solids content of the resin composition 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.

[0555] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used together, it is preferable that their combined dosage is within the range described above.

[0556] [Other crosslinking agents]

[0557] The resin composition of the present invention preferably also contains other crosslinking agents different from the free radical crosslinking agents described above.

[0558] Other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. 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-producing agents or photoalkali-producing agents. 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 acids or bases.

[0559] The acid or base mentioned above is preferably an acid or base generated by a photoacid generator or a photoalkali generator during the exposure process.

[0560] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0561] [Polymerization initiator]

[0562] In the resin composition of the present invention, there are no particular limitations on the photoradical polymerization initiator, which includes the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitizing to light from the ultraviolet region to the visible region is preferred. Furthermore, an active agent that generates active free radicals by interacting with a photoexcited sensitizer may also be used.

[0563] The photoradical polymerization initiator preferably contains at least one initiator having a wavelength range of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1The molar absorptivity of a compound can be determined using known methods. For example, it is preferable to use a UV-Vis spectrophotometer (a Cary-5 spectrophotometer manufactured by Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0564] As photoradical polymerization initiators, any known compounds can be used. Examples include haloalkanes (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, azide 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.

[0565] Examples of ketone compounds include, for instance, those described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, which are incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferred among commercially available products.

[0566] 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 are incorporated herein by reference.

[0567] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0568] 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 (all manufactured by BASF) can be used.

[0569] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 are also preferred. This content is incorporated herein by reference.

[0570] Oxime compounds are preferred as photoradical polymerization initiators. Using oxime compounds allows for more effective improvement in exposure latitude. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also function as photocuring accelerators.

[0571] 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. The compounds described in andTechnology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent Application Publication No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and the compounds described in International Publication No. 2013 / 167515, etc., are included in this specification.

[0572] Preferred oxime compounds include, for example, compounds with the following structures, or 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, etc. In resin compositions, oxime compounds are particularly preferred as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=NOC (=O)- linker group within the molecule.

[0573] [Chemical Formula 57]

[0574]

[0575] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Co.,Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Oxime compounds with the following structures can also be used.

[0576] [Chemical Formula 58]

[0577]

[0578] As photoradical polymerization initiators, for example, oxime compounds with fluorene rings, oxime compounds with at least one benzene ring forming a naphthalene ring skeleton, and oxime compounds with fluorine atoms can also be used.

[0579] Furthermore, oxime compounds with nitro groups, oxime compounds with benzofuran skeletons, and oxime compounds with hydroxyl substituents bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, can also be used. These contents are incorporated in this specification.

[0580] Furthermore, compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Publication No. 2023-058585 can also be used as photopolymerization initiators. This description is incorporated into the specification of this application.

[0581] When the resin composition contains a photopolymerization initiator, its content relative to the total solids content of the resin composition 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 contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range.

[0582] In addition, photopolymerization initiators sometimes also function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators can sometimes be further carried out by heating in an oven or heating plate.

[0583] [Sensitizer]

[0584] 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, thereby generating free radicals, acids, or bases.

[0585] 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 methylimine, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0586] Examples of sensitizers include mifepristone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminophenylenepropyl (cinnamyliden) e) Dihydroindanone, p-dimethylaminobenzyl dihydroindanone, 2-(p-dimethylaminophenylbenzyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylamino Coumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morphofolinylbenzophenone, isodimethylaminobenzoic acid Amyl ester, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0587] In addition, other sensitizing pigments can also be used.

[0588] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0589] 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.

[0590] [Chain transfer agent]

[0591] 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 Polymer Society, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecular -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc., with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferred.

[0592] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0593] When the resin composition contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids content of the resin composition 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. There may be only one type of chain transfer agent, or there may be two or more types. When there are two or more types of chain transfer agents, it is preferable that their total amount is within the above range.

[0594] Furthermore, the resin composition of the present invention containing two or more polymerization initiators is also one of the preferred embodiments of the present invention.

[0595] Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0596] By including a photopolymerization initiator and a thermal polymerization initiator described later, exposure-based patterning can be achieved, and free radical polymerization can be easily carried out during curing based on the heating process described later, sometimes improving properties such as chemical resistance.

[0597] As the ratio of the photopolymerization initiator and the thermal polymerization initiator (described later), the content of the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0598] By incorporating photoradical polymerization initiators and photoacid-producing agents, properties such as resolution can sometimes be improved.

[0599] As for the content ratio when photopolymerization initiator and photoacid generator are included, the content of photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of photopolymerization initiator and photoacid generator.

[0600] [Thermal polymerization initiator]

[0601] Examples of thermal polymerization initiators include thermal free radical polymerization initiators. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy to initiate or promote the polymerization reaction of polymerizable compounds. By adding thermal free radical polymerization initiators, polymerization reactions of resins and polymerizable compounds can also be carried out, thus further improving solvent resistance.

[0602] As thermal free radical polymerization initiators, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated in this specification, can be cited.

[0603] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition 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 be one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0604] <Alkali-producing agent>

[0605] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of producing alkali through physical or chemical action. Preferred alkali-generating agents include thermal alkali-generating agents and photo-alkali-generating agents.

[0606] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably 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, thereby improving the mechanical properties or chemical resistance of the cured product, such as improving its performance as an interlayer insulating film for rewiring layers included in semiconductor packages.

[0607] As an alkali-producing agent, it can be either an ionic or a nonionic alkali-producing agent. Examples of bases produced by alkali-producing agents include secondary and tertiary amines.

[0608] There are no particular limitations on the alkali-generating agent; any known alkali-generating agent can be used. Examples of known alkali-generating agents include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imine salts, pyridinium salts, α-lactone ring derivative compounds, amine imine compounds, phthalimide derivative compounds, and acyloxyimine compounds.

[0609] Specific compounds that can be cited as nonionic alkali-producing agents include those represented by formulas (B1), (B2), or (B3).

[0610] [Chemical Formula 59]

[0611]

[0612] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each of these can be used independently to represent an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. Among them, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2 and Rb 3 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 the carbon atoms of the hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is the carbon atom constituting the carbonyl group, that is, if an amide group is formed with the nitrogen atom, it is not a tertiary amine structure.

[0613] 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 ring and a condensed ring, preferably a monocyclic ring or a condensed ring obtained by the condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0614] More specifically, Rb 1 and Rb 2Preferably, the atom is hydrogen, alkyl (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (preferably with 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10) or aralkyl (preferably with 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). These groups may have substituents. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are 4- to 7-membered nitrogen-containing heterocycles. Rb 1 and Rb 2 Preferably, it is a straight-chain, branched, or cyclic alkyl group that may have substituents (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), more preferably a cycloalkyl group that may have substituents (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), and even more preferably a cyclohexyl group that may have substituents.

[0615] As Rb 3 Examples of such compounds include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), aralkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), aryl-alkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), and arylalkoxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Preferably, the compounds are cycloalkyl (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), aryl, or arylalkoxy. Rb 3 It can further have substituents.

[0616] The compound represented by formula (B1) is preferably the compound represented by formula (B1-1) or formula (B1-2) below.

[0617] [Chemical Formula 60]

[0618]

[0619] In the formula, Rb 11 and Rb 12and Rb 31 and Rb 32 respectively with Rb in equation (B1) 1 and Rb 2 same.

[0620] Rb 13 It is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), an alkenyl group (preferably with 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), an aryl group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an aralkyl group (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), and may have substituents. Rb 13 Preferably, it is an aryl alkyl group.

[0621] Rb 33 and Rb 34 Each 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.

[0622] Rb 35 The carbon atoms are alkyl (preferably 1 to 24, more preferably 1 to 12, and even more preferably 3 to 8), alkenyl (preferably 2 to 12, more preferably 2 to 10, and even more preferably 3 to 8), aryl (preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 12), aralkyl (preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 12), and preferably aryl.

[0623] The compound represented by formula (B1-1) is preferably the compound represented by formula (B1-1a).

[0624] [Chemical Formula 61]

[0625]

[0626] Rb 11 and Rb 12 Rb in equation (B1-1) 11 and Rb 12 The meanings are the same.

[0627] Rb 15 and Rb 16The atom is hydrogen, alkyl (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), aryl (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen or methyl.

[0628] Rb 17 The carbon atoms are alkyl (preferably 1 to 24, more preferably 1 to 12, and even more preferably 3 to 8), alkenyl (preferably 2 to 12, more preferably 2 to 10, and even more preferably 3 to 8), aryl (preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 12), or aralkyl (preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 12), wherein aryl is preferred.

[0629] [Chemical Formula 62]

[0630]

[0631] In formula (B3), L represents a hydrocarbon group, which is a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the connecting chain linking adjacent oxygen and carbon atoms, and the number of atoms in the connecting chain path is three or more. Furthermore, R... N1 and R N2 Each of these represents a monovalent organic group independently.

[0632] In this specification, a "linking chain" refers to the shortest (minimum number of atoms) chain connecting two atoms or groups of atoms in a path that links the linked objects. For example, in the compound represented by the following formula, L is composed of phenylene ethylene and has ethylene as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms in 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.

[0633] [Chemical Formula 63]

[0634]

[0635] 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, further preferably 10 or less, and especially preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above-described intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and especially preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds as alkali-producing 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.

[0636] Furthermore, the alkali-producing agent preferably includes a compound represented by the following formula (N1).

[0637] [Chemical Formula 64]

[0638]

[0639] In equation (N1), R N1 and R N2 Each of the following independently represents a monovalent organic group, R C1 The symbol represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0640] L is a divalent linker, preferably a divalent organic group. The linker chain length 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 linker chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0641] In equation (N1), R N1 and R N2 Each organic group, representing a single valence (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), is preferably a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include aliphatic hydrocarbon groups (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or aromatic hydrocarbon groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), with aliphatic hydrocarbon groups being preferred. If R is used as... N1 and R N2Using aliphatic hydrocarbon groups results in a highly basic base, which is therefore preferred. Furthermore, aliphatic and aromatic hydrocarbon groups can have substituents, and these groups can 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.

[0642] As a component of R N1 and R N2 Examples of aliphatic hydrocarbon groups include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups comprising combinations of chain alkyl groups 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.

[0643] 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.

[0644] The number of carbon atoms in the group comprising a combination of chain alkyl and cyclic alkyl groups is preferably 4 to 24, more preferably 4 to 18, and even more preferably 4 to 12. Examples of groups comprising a combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0645] 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.

[0646] From the perspective of increasing the boiling point of the alkali produced by the subsequent decomposition, R N1 and R N2 Alkyl groups with 5 to 12 carbon atoms are preferred. In formulations where adhesion with metal (e.g., copper) layers is important, alkyl groups having cyclic alkyl groups or alkyl groups with 1 to 8 carbon atoms are preferred.

[0647] R N1 and R N2 They can connect to each other to form a ring structure. The ring structure can contain oxygen atoms, etc., within the chain. Furthermore, R... N1 and R N2The formed ring structure can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. The formed ring structure is preferably a 5-membered or 6-membered ring containing a nitrogen atom as in 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 particularly preferred.

[0648] R C1 It represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0649] As a protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid is a preferred example.

[0650] 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, preferably methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxycyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP).

[0651] In formula (N1), the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have substituents, or may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have oxygen atoms in the chain, further preferably a divalent aliphatic hydrocarbon group that may have oxygen atoms in the chain, a divalent aromatic hydrocarbon group, or a group comprising a combination of a divalent aliphatic hydrocarbon group that may have oxygen atoms in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have oxygen atoms in the chain. These groups may not have oxygen atoms.

[0652] 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 comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylene alkyl group) is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0653] Specifically, the linker L is preferably a linear or branched chain alkylene, a cyclic alkylene, a group comprising a combination of linear and cyclic alkylene, an alkylene having an oxygen atom in the chain, a linear or branched chain alkenylene, a cyclic alkenylene, an arylene, or an arylalkylene.

[0654] 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.

[0655] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6.

[0656] The number of carbon atoms in the group comprising a combination of chain alkylene and cyclic alkylene is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0657] The alkylene group having 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 having oxygen atoms in the chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0658] 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.

[0659] 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.

[0660] 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.

[0661] The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.

[0662] Preferably, the alkylene group is a chain-like alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain-like alkenyl group, an arylene group, or an aryl alkylene group; more preferably, it is 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), or ethoxyethylene (especially 1,2-ethoxy-1,2-ethylene).

[0663] The following compounds can be cited as alkali-producing agents, but are not limited to these.

[0664] [Chemical Formula 65]

[0665]

[0666] [Chemical Formula 66]

[0667]

[0668] The molecular weight of the nonionic alkali-generating agent is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0669] Specific preferred compounds as ionic alkali-generating agents include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0670] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[0671] [Chemical Formula 67]

[0672]

[0673] The following compounds can be cited as specific examples of imine salts, but are not limited to these.

[0674] [Chemical Formula 68]

[0675]

[0676] Furthermore, from the viewpoint of storage stability and the generation of alkali during curing deprotection, an amine with the amino group protected by a tert-butyloxycarbonyl group is preferred as an alkali-generating agent.

[0677] Examples of amine compounds protected by the tert-butyloxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)-1-propanol, 3-isopropylamino)propanol, N-cyclohexylethanolamine, and α-[2-(methylamino)-1-propanol, 3-amino-2-propanol, 3-amino-2-methyl-1-propanol, 3-amino-2 ... Compounds containing [amino(ethyl)benzyl alcohol], diethanolamine, diisopropanolamine, 3-pyrrolidone, 2-pyrrolidone methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidine methanol, 3-piperidine methanol, 2-piperidine methanol, 4-piperidine ethanol, 2-piperidine ethanol, 2-(4-piperidine)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy) ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecanane, or amino acids and their derivatives whose amino group is protected by a tert-butyloxycarbonyl group, but not limited to these.

[0678] When the resin composition contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of resin in the resin composition. 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, even more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and particularly preferably 4 parts by weight or less.

[0679] One or more alkali-generating agents can be used. When using two or more, it is preferable that the total amount is within the above range.

[0680] <Solvent>

[0681] The resin composition of the present invention preferably contains a solvent.

[0682] 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.

[0683] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-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, alkyl 3-alkoxypropionate). Ethyl propionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[0684] Examples of preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether 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.

[0685] Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydro L-glucanone.

[0686] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred cyclic hydrocarbons.

[0687] As a sulfoxide, dimethyl sulfoxide can be cited as a preferred sulfoxide.

[0688] As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine are among the preferred amides.

[0689] Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are preferred ureas.

[0690] 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, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0691] From the perspective of improving the properties of the coating surface, it is also preferable to use a mixture of two or more solvents.

[0692] In this invention, the solvent is preferably selected from one of the following: 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, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucosidone, and dihydroL-glucosidone, or a mixed solvent consisting of two or more of these solvents. Particularly preferred methods include the use of dimethyl sulfoxide with γ-butyrolactone, dimethyl sulfoxide with γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone with ethyl lactate. Further addition of approximately 1 to 10% by mass relative to the total mass of these solvents is also a preferred method of the invention.

[0693] In particular, from the viewpoint of the storage stability of the resin composition, including γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, there is no particular upper limit to the above content, and it can be 100% by mass. Regarding the above content, it can be determined by taking into account the solubility of specific resin components or other components contained in the resin composition.

[0694] Furthermore, when using dimethyl sulfoxide and γ-valerolactone together, the total mass of the solvent preferably contains 60-90% by mass of γ-valerolactone and 10-40% by mass of dimethyl sulfoxide, more preferably 70-90% by mass of γ-valerolactone and 10-30% by mass of dimethyl sulfoxide, and even more preferably 75-85% by mass of γ-valerolactone and 15-25% by mass of dimethyl sulfoxide.

[0695] Furthermore, the resin composition of the present invention preferably contains a solvent with a boiling point of 50°C to 300°C at 1 atmosphere, and more preferably contains a solvent with a boiling point of 100°C to 260°C. In the present invention, the boiling point of the solvent is the boiling point at 1 atmosphere.

[0696] Based on this method, it is believed that cured products with excellent solvent removal and high resolution can be obtained.

[0697] The boiling point is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The upper limit of the boiling point is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower.

[0698] Furthermore, the resin composition of the present invention preferably contains two or more solvents with boiling points of 100 to 260°C, more preferably two or more solvents with boiling points of 150 to 250°C, and even more preferably two or more solvents with boiling points of 180 to 230°C.

[0699] Furthermore, the content of solvents with boiling points of 100 to 260°C is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more relative to the total mass of the composition. When two or more solvents with boiling points of 100 to 260°C are included, it is preferable that their total amount is within the above-mentioned range.

[0700] From the viewpoint of coatability, it is preferable to set the solvent content to an amount that is 5 to 80% by mass of the total solids concentration of the resin composition of the present invention, 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 desired thickness of the coating and the coating method. When two or more solvents are contained, it is preferable that their total amount is within the above range.

[0701] <Metal Adhesion Modifier>

[0702] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, the resin composition of the present invention preferably includes a metal adhesion modifier. 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-ketoester compounds, and amino compounds.

[0703] [Silane coupling agent]

[0704] Examples of silane coupling agents include, for instance, compounds described in paragraph 0316 of International Patent Publication No. 2021 / 112189 and compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, it is preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl. Furthermore, the following R can be a structure derived from the blocking agent in the isocyanate group. As the blocking agent, it can be selected according to the deactivation temperature; examples include alcohol compounds, phenolic compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the deactivation temperature to 160–180°C, caprolactam is preferred. Commercially available examples of this compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0705] [Chemical Formula 69]

[0706]

[0707] [Chemical Formula 70]

[0708]

[0709] 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-acryloyloxypropyltrimeth ... The following are listed: 3-aminopropyltrimethoxysilane, 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-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0710] Furthermore, oligomer-type compounds having multiple alkoxysilane groups can also be used as silane coupling agents.

[0711] Examples of such oligomer-type compounds include compounds containing repeating units represented by the following formula (S-1).

[0712] [Chemical Formula 71]

[0713]

[0714] In equation (S-1), R S1 R represents a monovalent organic group. S2 It represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer from 0 to 2.

[0715] R S1The preferred structure includes a polymerizable group. Examples of polymerizable groups include groups having an olefinic unsaturated bond, epoxy groups, cyclobutane groups, benzoxazolyl groups, terminal isocyanate groups, and amino groups. Examples of groups having an olefinic unsaturated bond include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, etc., preferably vinylphenyl, (meth)acrylamido, or (meth)acryloyloxy, more preferably vinylphenyl or (meth)acryloyloxy, and even more preferably (meth)acryloyloxy.

[0716] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[0717] n represents an integer from 0 to 2, preferably 1.

[0718] Here, the structures of the repeating units represented by the multiple formulas (S-1) contained in the oligomer type compound can be the same.

[0719] Here, in the oligomer-type compound, at least one of the repeating units represented by the plurality of formulas (S-1) contains n is preferably 1 or 2, more preferably at least two in which n is 1 or 2, and even more preferably at least two in which n is 1.

[0720] As such oligomer-type compounds, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0721] [Aluminum-based adhesive additives]

[0722] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate aluminum diisopropyl ester.

[0723] 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 incorporated in this specification.

[0724] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the content to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting the content to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. There may be only one type of metal adhesion modifier, or there may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0725] <Migration Inhibitor>

[0726] The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, for example when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0727] 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), compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0728] Among these, the resin composition of the present invention preferably contains an azole compound.

[0729] Azole compounds are compounds containing a azole structure, which refers to a 5-membered ring structure containing a nitrogen atom as a cyclic atom, preferably a 5-membered ring structure containing two or more nitrogen atoms as cyclic atoms. Specifically, examples of azole structures include imidazole, triazole, and tetraazole structures. Like benzimidazole and benzotriazole, these structures can form polycyclic rings with other ring structures through condensation or other processes.

[0730] Furthermore, as a compound having an azole structure, it is preferred to be a compound having a group represented by the following formula (R-1) or the following formula (R-2) directly bonded to the azole structure.

[0731] [Chemical Formula 72]

[0732]

[0733] In equation (R-1), R1 The symbol represents a monovalent organic group, and * indicates the bonding site with the azole structure.

[0734] In equation (R-2), R 2 R represents a hydrogen atom or a monovalent organic group. 3 The symbol represents a monovalent organic group, and * indicates the bonding site with the azole structure.

[0735] In equation (R-1), R 1 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A base represented by a bond of at least one type of base in the group that makes up the group. R N As stated above.

[0736] The aforementioned hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these groups.

[0737] Furthermore, R 1 The total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0738] R 1 The bonding site between the carbonyl group in formula (R-1) and the carbonyl group is preferably a hydrocarbon group or -NR. N -

[0739] In formula (R-1), * represents the bonding site with the azole structure, preferably the bonding site with the carbon atom that forms the cyclization of the azole structure.

[0740] In equation (R-2), R 2 Hydrogen atoms are preferred.

[0741] In R 2 When R is a monovalent organic group, 2 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A base represented by a bond of at least one type of base in the group that makes up the group. R N As stated above.

[0742] The aforementioned hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these groups.

[0743] Furthermore, R 2 When the organic group is monovalent, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0744] In R 2 When R is a monovalent organic group, 2The bonding site between the nitrogen atom in formula (R-2) and the nitrogen atom is preferably a hydrocarbon group or -C(=O)-.

[0745] In equation (R-2), R 3 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A base represented by a bond of at least one type of base in the group that makes up the group. R N It represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom.

[0746] The aforementioned hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these groups.

[0747] Furthermore, R 3 When the organic group is monovalent, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.

[0748] R 3 The bonding site between the nitrogen atom in formula (R-2) and the nitrogen atom is preferably a hydrocarbon group or -C(=O)-.

[0749] In formula (R-2), * represents the bonding site with the azole structure, preferably the bonding site with the carbon atom that forms the cyclization of the azole structure.

[0750] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0751] Other migration inhibitors include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are incorporated herein by reference.

[0752] The following compounds can be cited as specific examples of migration inhibitors.

[0753] [Chemical Formula 73]

[0754]

[0755] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass relative to the total solid content of the resin composition, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0756] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number falls within the range mentioned above.

[0757] <Light Absorber>

[0758] The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.

[0759] Examples of light absorbers include compounds described in paragraphs 0159 to 0183 of International Patent Publication No. 2022 / 202647 and compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are included in this specification.

[0760] In particular, from the viewpoint of improving adhesion to the substrate, the resin composition of the present invention preferably further comprises the above-mentioned azole compound and the above-mentioned silane coupling agent. By containing these compounds, adhesion to the substrate is easily maintained, especially even after the cured product is exposed to high temperature and high humidity conditions.

[0761] <Polymerization Inhibitor>

[0762] 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.

[0763] Specific compounds that can be cited as polymerization inhibitors include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is incorporated herein by reference.

[0764] 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 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.

[0765] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that their total number is within the range mentioned above.

[0766] <Other Additives>

[0767] The resin composition of the present invention may contain various additives as needed, within the range required to achieve the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, 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. These components can be described, for example, by referring to paragraph 0183 onwards in 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 used, it is preferable that their total content be set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0768] [surfactants]

[0769] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0770] By including a surfactant in the resin composition of the present invention, the liquid properties (especially flowability) during the preparation of the coating liquid composition can be further improved, thereby further improving the uniformity of the coating thickness and the liquid-saving properties. That is, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and enhancing the coating properties. Therefore, it is more preferable to form a uniform film with small thickness non-uniformity.

[0771] As fluorinated surfactants, compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which is incorporated herein by reference, can be cited.

[0772] As a fluorinated surfactant, a fluorinated polymer compound is also preferred, which comprises: repeating units derived from a (meth)acrylate compound having fluorine atoms; and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or glycidyl), for example, the following compounds.

[0773] [Chemical Formula 74]

[0774]

[0775] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0776] 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 DICCorporation.

[0777] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. From the viewpoint of uniformity of coating thickness and liquid-saving properties, fluorinated surfactants with fluorine content in this range are effective and have good solubility in the composition.

[0778] As silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants, examples include compounds described in paragraphs 0329 to 0334 of International Patent Publication No. 2021 / 112189, the contents of which are incorporated herein by reference.

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

[0780] The content of surfactant 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] [Inorganic particles]

[0782] Specifically, inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0783] The average particle size of the 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.

[0784] The aforementioned average particle size of the inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be determined, for example, by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO.,LTD.).

[0785] In cases where 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.

[0786] [Organotitanium compounds]

[0787] By incorporating organotitanium compounds into the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0788] As usable organotitanium compounds, examples include organotitanium compounds in which organic groups are covalently or ionicly bonded to titanium atoms.

[0789] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0790] I) Titanium chelate compounds: From the perspective of excellent storage stability of the resin composition and the ability to obtain a good cured pattern, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples are bis(triethanolamine)diisopropoxy titanium, bis(2,4-glutarate)di(n-butoxy) titanium, bis(2,4-glutarate)diisopropoxy titanium, bis(tetramethylheptyl ester)diisopropoxy titanium, bis(ethyl acetoacetate)diisopropoxy titanium, etc.

[0791] 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, tetrastearoyloxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0792] III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, 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.

[0793] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzene sulfonate) isopropoxy titanium, etc.

[0794] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0795] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0796] VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0797] From the viewpoint of better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dicarboxylated titanium compounds is preferred as the organotitanium compound. In particular, bis(ethyl acetoacetate)diisopropoxy titanium, tetra(n-butoxy) titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium are preferred.

[0798] Furthermore, it is also preferred to include, as an organotitanium compound or instead of an organotitanium compound, a compound represented by the following formula (T-1).

[0799] [Chemical Formula 75]

[0800]

[0801] In equation (T-1), M represents titanium, zirconium, or hafnium; l1 is an integer from 0 to 2; l2 is 0 or 1; l1 + l2 × 2 is an integer from 0 to 2; m is an integer from 0 to 4; n is an integer from 0 to 2; l1 + l2 + m + n × 2 = 4; R 11 R is independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted phenoxy. 12 R represents a substituted or unsubstituted hydrocarbon group. 2 Let R be a base that independently contains the structure represented by the following equation (T-2). 3 Let X be a base that independently contains the structure represented by the following equation (T-2). A Each can be an oxygen atom or a sulfur atom, independently.

[0802] [Chemical Formula 76]

[0803]

[0804] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, with * indicating the bonding site with other structures and # indicating the bonding site with metal atoms.

[0805] In formula (T-1), from the viewpoint of the storage stability of the composition, M is preferably titanium.

[0806] In equation (T-1), the setting of l1 and l2 to 0 is also one of the preferred embodiments of the present invention.

[0807] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0808] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0809] In this case, it is also preferable that l1 and l2 are 0 and m is 0, 2 or 4 in equation (T-1).

[0810] In equation (T-1), from the perspective of the stability of a specific metal complex, R 11 Preferably, it is a substituted or unsubstituted cyclopentadiene ligand.

[0811] Furthermore, R 11 The cyclopentadienyl, alkoxy, and phenoxy groups in the present invention can be substituted, but the unsubstituted form is also one of the preferred forms of the present invention.

[0812] In equation (T-1), R 12 Preferably, it is a hydrocarbon group with 1 to 20 carbon atoms, and more preferably a hydrocarbon group with 2 to 10 carbon atoms.

[0813] As R 12 The hydrocarbon group in the form can be any one of aliphatic hydrocarbon group or aromatic hydrocarbon group, but is preferably an aromatic hydrocarbon group.

[0814] As an aliphatic hydrocarbon group, it can be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0815] As an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 10 carbon atoms, and even more preferably a phenylene group.

[0816] As R 12 The substituents in R are preferably monovalent substituents, such as halogen atoms. Furthermore, in R... 12 In the case of aromatic hydrocarbon groups, alkyl groups can be used as substituents.

[0817] Among these, in equation (T-1), R 12 Preferably, it is an unsubstituted phenylene oxide. Furthermore, R 12 The phenylene oxide in the sample is preferably 1,2-phenylene oxide.

[0818] In equation (T-1), when m is 2 or more and contains more than 2 R... 2 In the case of two or more R 2 The structures can be the same or different.

[0819] In equation (T-1), when n is 2 or more and contains more than 2 R... 3 In the case of two or more R 3 The structures can be the same or different.

[0820] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, preferably at least one of them is -C(-*)=, more preferably at least two of them are -C(-*)=.

[0821] As specific examples of compounds represented by formula (T-1), compounds corresponding to I-3 in the examples can be cited, but are not limited to these.

[0822] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of a specific resin. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when the content is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0823] When an organotitanium compound is included, its content 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 content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when the content is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0824] Other additives include compounds described in paragraphs 0249–0282 and 0316–0358 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0825] <Characteristics of the Resin Composition>

[0826] 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. If within the above range, a highly uniform coating film can be easily obtained. For example, if it is 1,000 mm... 2 If the speed is above 12,000 mm, it is easy to coat with the film thickness required for reinsertion insulation. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0827] When a cured material with a film thickness of 10 μm is formed using the resin composition of the present invention, the transmittance of the cured material at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.

[0828] There is no specific upper limit to the above transmittance; it can be 100%.

[0829] The aforementioned cured product can be obtained, for example, by coating the resin composition of the present invention onto a silicon wafer, drying it at 100°C for 5 minutes, and then passing it through an i-ray at 500 mJ / cm². 2 After full-area exposure at the required exposure energy, the temperature is increased at a rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 180 minutes.

[0830] <Restrictions on the Contents of Substances in Resin Compositions>

[0831] 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. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0832] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[0833] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably 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 in the form of complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above-described range.

[0834] Furthermore, as a method to reduce unintentionally contained metal impurities in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention using a filter; and performing distillation in an apparatus lined with polytetrafluoroethylene or the like to suppress contamination as much as possible.

[0835] 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. Of this, the content existing in the form of 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. Preferably, the total amount of chlorine atoms and bromine atoms, or the total amount of chloride ions and bromide ions, is within the above-mentioned ranges.

[0836] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0837] As a container for the resin composition of the present invention, conventionally known containers can be used. It is also preferable to use a multi-layered bottle with an inner wall composed of six layers of six different resins, or a bottle in which the six resins are formed into a seven-layer structure, to prevent impurities from contaminating the raw materials or the resin composition of the present invention. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0838] <Cure of Resin Composition>

[0839] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0840] The cured product of the present invention is a cured product obtained by curing a resin composition.

[0841] The curing of the resin composition is preferably carried out by heating, more preferably at a heating temperature of 120°C to 400°C, further preferably at 140°C to 380°C, and particularly preferably at 170°C to 350°C. The cured form of the resin composition is not particularly limited, and can be film-shaped, rod-shaped, spherical, granular, etc., depending on the application. In this invention, the cured form is preferably film-shaped. The shape of the cured form can also be selected by patterning the resin composition, depending on the application such as forming a protective film on a wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, or imparting heat dissipation. The film thickness of the cured form (the film formed by the cured form) is preferably 0.5 μm or more and 150 μm or less.

[0842] The shrinkage rate during curing of the resin composition of the present invention 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 by the following formula.

[0843] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0844] <Characteristics of cured resin compositions>

[0845] 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. If it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[0846] 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.

[0847] 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.

[0848] <Preparation of Resin Compositions>

[0849] The resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited and can be carried out using conventionally known methods.

[0850] Examples of mixing methods include mixing based on stirring blades, mixing based on ball mills, and mixing by rotating a tank.

[0851] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0852] The purpose of filtration is preferably to remove foreign matter such as dust or particles from the resin composition of the present invention. The filter pore size is preferably 5 μm or less, more preferably 1 μm or less, further preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The 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. Multiple filters can be connected in series or in parallel during the filtration process. When using multiple filters, filters with different pore sizes or materials can be used in combination. For example, a connection method can be as follows: an HDPE filter with a pore size of 1 μm is used as the first stage, and an HDPE filter with a pore size of 0.2 μm is used as the second stage, and the two are connected in series. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, cyclic filtration can be used. Furthermore, filtration can be performed by pressurization. When filtration is performed by pressurization, the applied pressure is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even 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.

[0853] In addition to filtration using filters, impurities can also be removed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. 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.

[0854] Alternatively, after filtration using a filter, the resin composition filled in the bottle can be placed under reduced pressure and degassed.

[0855] (Method for manufacturing solidified products)

[0856] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.

[0857] The method for manufacturing the cured material 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.

[0858] The method for manufacturing the cured material is particularly preferably 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.

[0859] Furthermore, the method for manufacturing the cured material preferably includes the above-mentioned film formation process and the process of heating the above-mentioned film.

[0860] The following is a detailed explanation of each process.

[0861] <Membrane Formation Process>

[0862] The resin composition of the present invention can be used in a film forming process applied to a substrate to form a film.

[0863] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.

[0864] [Substrate]

[0865] The type of substrate can be appropriately selected according to the application and is not particularly limited. Examples of substrates include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, any of the substrates formed of metal and substrates with metal layers formed by plating, vapor deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). Regarding substrates, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[0866] Alternatively, a close-bonding layer or oxide layer formed of hexamethyldisilazane (HMDS) or similar material can be provided on the surface of these substrates.

[0867] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[0868] Regarding the dimensions of the substrate, if it is circular, the diameter is preferably 100–450 mm, more preferably 200–450 mm. If it is rectangular, the length of the shorter side is preferably 100–1000 mm, more preferably 200–700 mm.

[0869] As a substrate, for example, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0870] When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer formed by curing) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0871] As a method for applying a resin composition to a substrate, coating is preferred.

[0872] Specifically, methods for application 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 is preferred. From the viewpoints of film thickness uniformity and productivity, spin coating and slot coating are more preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the application 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 is preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating is preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

[0873] Furthermore, it is also possible to apply a method for transferring a coating formed by pre-applying it to a temporary support through the above-described application method onto a substrate.

[0874] Regarding the transfer method, the production 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 preferred.

[0875] Furthermore, a process can be performed to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinse (EBR) and back-side rinse.

[0876] The following pre-wetting process can be used: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0877] <Drying Process>

[0878] After the film formation process (layer formation process), in order to remove the solvent, the above-mentioned film can be used for a process of drying the formed film (layer) (drying process).

[0879] 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.

[0880] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0881] The drying temperature of the membrane in the drying process is preferably 50–150°C, more preferably 70–130°C, and even more preferably 90–110°C. Furthermore, drying can also be performed under reduced pressure. Examples of drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0882] <Exposure Process>

[0883] The above-mentioned film can be used in an exposure process for selective exposure of the film.

[0884] The method for manufacturing a cured material may include an exposure process that selectively exposes a film formed by a film forming process.

[0885] Selective exposure refers to exposing only a portion of the film. Furthermore, by selective exposure, exposed areas (exposed areas) and unexposed areas (non-exposed areas) are formed on the film.

[0886] Regarding the exposure amount, there is no particular limitation as long as it is sufficient to cure the resin composition of the present invention, but for example, when calculated 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 .

[0887] The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0888] 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 (gamma, h, i-rays, etc.), (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) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. For the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and from the viewpoint of exposure sensitivity, exposure based on i-rays is more preferred.

[0889] There is no particular limitation on the exposure method, as long as at least a portion of the film formed by the resin composition of the present invention is exposed. Examples include exposure using a photomask and exposure based on direct laser imaging.

[0890] <Post-exposure heating process>

[0891] The above-mentioned film can be used in the process of heating after exposure (post-exposure heating process).

[0892] 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.

[0893] The post-exposure heating process can be performed after the exposure process and before the development process.

[0894] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0895] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0896] From the initial heating temperature to the maximum heating temperature, the heating rate during the post-exposure heating process is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0897] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0898] There are no particular limitations on the heating mechanism used in the post-exposure heating process; commonly known heating plates, ovens, infrared heaters, etc., can be used.

[0899] Furthermore, it is preferable to conduct the heating process in an atmosphere with a low oxygen concentration by circulating inert gases such as nitrogen, helium, or argon.

[0900] <Developing Process>

[0901] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0902] That is, the method for manufacturing the cured material 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.

[0903] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0904] Here, the development process that removes the non-exposed portions of the film is called negative development, and the development process that removes the exposed portions of the film is called positive development.

[0905] [Developing solution]

[0906] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0907] When the developer is an alkaline aqueous solution, examples of alkaline compounds that can be included in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is preferred. In the total mass of the developer, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0908] When the developer contains an organic solvent, compounds described in paragraph 0387 of International Publication No. 2021 / 112189 may be used as the organic solvent. This content is incorporated into this specification. Furthermore, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., are preferably included as alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., are preferably included as amides.

[0909] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, more preferably a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and especially preferably a developer containing cyclopentanone.

[0910] 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 may also be 100% by mass.

[0911] The developer may further contain other ingredients.

[0912] Other components include, for example, well-known surfactants or well-known defoamers.

[0913] [Method for supplying developer]

[0914] 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, and examples include straight nozzles, shower nozzles, and spray nozzles.

[0915] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to use a method of supplying developer using a straight nozzle or a method of continuous supply using a spray nozzle. From the viewpoint of developer penetration into the image area, it is more preferable to use a method of supplying using a spray nozzle.

[0916] Furthermore, the process can be performed by continuously supplying developer using a straight nozzle, rotating the substrate and removing the developer from the substrate, performing rotary drying, and then continuously supplying developer again using a straight nozzle, rotating the substrate and removing the developer from the substrate. This process can be repeated multiple times.

[0917] Methods for supplying developer in the developing process include processes such as continuously supplying developer to a substrate, maintaining developer on a substrate in a substantially static state, using ultrasound or the like to vibrate developer on a substrate, and combining these methods.

[0918] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0919] In the developing process, after treatment with the developer, the pattern can be further cleaned (rinsed) using a rinsing solution. Furthermore, methods such as supplying the rinsing solution before the developer in contact with the pattern has completely dried can be employed.

[0920] [Rinse solution]

[0921] 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.

[0922] When the rinsing solution contains an organic solvent, examples of organic solvents that are the same as those exemplified when the developing solution contains an organic solvent can be given.

[0923] The organic solvent contained in the rinsing solution is preferably an organic solvent that is different from the organic solvent contained in the developing solution, and more preferably an organic solvent that has a lower solubility for the pattern compared to the organic solvent contained in the developing solution.

[0924] When the rinsing solution contains an organic solvent, one or more organic solvents may be used. Preferred organic solvents are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME; more preferably, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME; and even more preferably, cyclohexanone and PGMEA.

[0925] When the rinsing solution contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more relative to the total mass of the rinsing solution. Furthermore, the organic solvent may also be 100% by mass relative to the total mass of the rinsing solution.

[0926] The rinsing solution may further contain other ingredients.

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

[0928] [Method for supplying flushing fluid]

[0929] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. Methods include immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by holding the liquid, supplying the rinsing liquid to the substrate by spraying, and continuously supplying the rinsing liquid to the substrate using a mechanism such as a straight nozzle.

[0930] From the viewpoints of penetrability of the rinsing fluid, removal of non-image areas, and manufacturing efficiency, there are methods for supplying rinsing fluid using spray nozzles, straight nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred, and from the viewpoint of penetrability of the rinsing fluid to the image area, a method using a mist nozzle is even more preferred. There are no particular limitations on the type of nozzle; examples include straight nozzles, shower nozzles, and spray nozzles.

[0931] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed film using a straight nozzle, and more preferably a process of supplying rinsing liquid using a spray nozzle.

[0932] As a method for supplying rinsing fluid in the rinsing process, methods such as continuously supplying rinsing fluid to the substrate, maintaining the rinsing fluid on the substrate in a substantially static state, vibrating the rinsing fluid on the substrate using ultrasound or the like, and combining these methods are all possible.

[0933] 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 is preferably 10 to 45°C, more preferably 18 to 30°C.

[0934] <Heating Process>

[0935] The pattern obtained by the developing process (or the washed pattern in the case of the washing process) can be used in a heating process for heating the pattern obtained by the developing process described above.

[0936] 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.

[0937] Furthermore, the method for manufacturing the cured product of the present invention may also 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.

[0938] During the heating process, resins such as polyimide precursors are cyclized to become resins such as polyimide.

[0939] Furthermore, crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed.

[0940] 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, even more preferably 160 to 250°C, and especially preferably 160 to 230°C.

[0941] The heating process is preferably a process in which the cyclization reaction of the polyimide precursor is promoted within the pattern by heating and utilizing the action of the alkali or the alkali produced by the alkali-generating agent.

[0942] From the initial heating temperature to the maximum heating temperature, the heating process is preferably carried out at a heating rate of 1 to 12°C / minute. 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, excessive evaporation of acid or solvent can be prevented while ensuring productivity, and by setting the heating rate to 12°C / minute or less, residual stress in the cured product can be mitigated.

[0943] 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.

[0944] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the heating process begins and continues until the maximum heating temperature is reached. For example, in the case of drying the resin composition of the present invention after applying it to a substrate, it is the temperature of the dried film (layer), preferably starting at a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0945] 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.

[0946] In particular, when forming a multi-layered 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.

[0947] The upper limit of the above heating temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

[0948] 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, holding at 120°C for 60 minutes, and then heating from 120°C to 180°C at a rate of 2°C / min, holding at 180°C for 120 minutes. Furthermore, it is also preferable to perform the treatment while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. This pretreatment process can improve the properties of the membrane. The pretreatment process only needs to be performed for a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be a two-stage or more process; for example, the first stage of the pretreatment process can be performed in the range of 100–150°C, followed by the second stage of the pretreatment process in the range of 150–200°C.

[0949] Alternatively, heating followed by cooling can be performed, with a preferred cooling rate of 1 to 5°C / minute.

[0950] Regarding the heating process, from the viewpoint of preventing the decomposition of specific resins, it is preferable to carry out the process in an atmosphere with a low oxygen concentration by circulating inert gases such as nitrogen, helium, or argon, or by conducting the process under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0951] There are no particular limitations on the heating mechanism in the heating process, but examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0952] <Post-development exposure process>

[0953] The pattern obtained by the developing process (or the washed pattern in the case of a washing process) can be used in a post-developing exposure process to expose the pattern after the developing process, instead of the heating process described above or in addition to the heating process described above.

[0954] 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.

[0955] In the post-development exposure process, it can promote, for example, the cyclization reaction of polyimide precursors by photo-alkali-generating agents and the removal of acid-degrading groups by photo-acid-generating agents.

[0956] In the post-development exposure process, it is sufficient for at least a portion of the pattern obtained in the development process to be exposed, but it is preferable for all of the pattern to be exposed.

[0957] 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 .

[0958] The post-development exposure process can be performed using the light source described in the above-mentioned exposure process, preferably broadband light.

[0959] <Metal Layer Formation Process>

[0960] The pattern obtained by the developing process (preferably a pattern for at least one of the heating process and the post-development exposure process) can be used in the metal layer forming process for forming a metal layer on the pattern.

[0961] 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 a pattern provided for at least one of a heating step and a post-developing exposure step).

[0962] 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 more preferred, and copper is even more preferred.

[0963] There are no particular limitations on the method for forming the metal layer, 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 or copper cyanide plating solutions can be cited.

[0964] The thickness of the metal layer is preferably 0.01 to 50 μm in the thickest part, and more preferably 1 to 10 μm.

[0965] <Uses>

[0966] Examples of applications for manufacturing methods or cured products to which the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress-relief films. Furthermore, examples include patterning sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or insulating films for mounting purposes as described above, by etching. For applications of these, please refer to, for example, SCIENCE AND TECHNOLOGY CO.,LTD. “High Functionalization and Application Technology of Polyimide”, April 2008, supervised by Masaaki Kakimoto; CMC Technical Library “Fundamentals and Development of Polyimide Materials”, November 2011; and the Japan Polyimide and Aromatic Polymer Symposium / ed., “Latest Polyimide Fundamentals and Applications”, NTS Inc., August 2010.

[0967] 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 molded parts in etching, and the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0968] (Laminated bodies and methods for manufacturing laminated bodies)

[0969] The laminate of the present invention refers to a structure having multiple layers formed by the cured product of the present invention.

[0970] A laminate is a laminate consisting of two or more layers formed by a solidified material, or it can be a laminate consisting of three or more layers.

[0971] In the above-described laminate, at least one of the two or more layers formed by the cured material is a layer 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 accompanying the shrinkage, it is also preferable that all the layers formed by the cured material included in the above-described laminate are layers formed by the cured material of the present invention.

[0972] 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 method for manufacturing the cured product of the present invention by repeating the process multiple times.

[0973] The laminate of the present invention preferably comprises two or more layers formed of a cured material, and a metal layer is included between any of the layers formed of the cured material. The metal layer is preferably formed by the aforementioned metal layer forming process.

[0974] That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer forming step during the process of manufacturing multiple 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.

[0975] As an example of the aforementioned laminate, a preferred laminate may be one that includes at least the following layer structure, wherein the layer structure is formed by sequentially stacking three layers: a layer formed by a first cured material, a metal layer, and a layer formed by a second cured material.

[0976] The layers formed by the first cured product and the layers formed by the second cured product are preferably both 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 can 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.

[0977] <Layering Process>

[0978] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0979] The lamination process includes a series of steps comprising performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step on the surface of a pattern (resin layer) or a metal layer. Alternatively, at least one of (a) the film formation step, (d) the heating step, and the post-development exposure step may be repeated. Furthermore, (e) the metal layer formation step may be included after at least one of (d) the heating step and the post-development exposure step. The lamination process may, of course, further appropriately include the aforementioned drying step, etc.

[0980] If a further lamination process is performed 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 can be cited as an example of surface activation treatment. Details regarding surface activation treatment will be described later.

[0981] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0982] For example, a preferred structure is one in which the resin layer is set to 2 or more but less than 20 layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and a more preferred structure is one in which the resin layer is set to 2 or more but less than 9 layers.

[0983] The composition, shape, and film thickness of each of the above layers can be the same or different.

[0984] In this invention, it is particularly preferred that, after the metal layer is formed, a cured product (resin layer) of the resin composition of the present invention is further formed by covering the metal layer. Specifically, examples include repeating at least one of (a) a film forming step, (b) an exposure step, (c) a development step, (d) a heating step and a post-development exposure step, and (e) a metal layer forming step, or repeating at least one of (a) a film forming step, (d) a heating step and a post-development exposure step, and (e) a metal layer forming step. By alternately performing the lamination step of the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[0985] (Surface activation treatment process)

[0986] 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 metal layer and the resin composition layer.

[0987] 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.

[0988] 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, at least a portion of the metal layer is surface activated, and more preferably, a portion or all of the region of the metal layer on which the resin composition layer is formed is surface activated. Thus, by surface activating the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on that surface can be improved.

[0989] It is preferable to also perform surface activation treatment 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 composition layer, the adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. In particular, when the resin composition layer has been cured, such as in the case of negative development, it is less susceptible to damage caused by surface treatment, and the adhesion is easily improved.

[0990] Regarding surface activation treatment, it can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0991] (Semiconductor devices and their manufacturing methods)

[0992] The present invention also discloses a semiconductor device comprising the cured material or laminate of the present invention.

[0993] Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product or the method for manufacturing a laminate of the present invention.

[0994] As a specific example of using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer in a semiconductor device, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in FIG1, which are incorporated herein by reference.

[0995] (Resin)

[0996] The resin of the present invention comprises repeating units represented by the following formula (1-1).

[0997] [Chemical Formula 77]

[0998]

[0999] In equation (1-1), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 3 and R 4 Each of the following expressions (R-1) represents the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

[1000] [Chemical Formula 78]

[1001]

[1002] In equation (R-1), L 1 A represents a linker base with valence a1+1. 1 The structure represented by equation (P-1) or (P-2) is given, where a1 represents an integer greater than 1, and * represents the structure related to X in equation (1-1). 1 Or Y 1 The bonding sites.

[1003] [Chemical Formula 79]

[1004]

[1005] In equation (P-1), R P1 The symbol represents a monovalent organic group, n represents an integer from 0 to 4, and * represents the L in formula (R-1). 1 The bonding sites.

[1006] In equation (P-2), R P2 Each of the above represents a hydrogen atom or a monovalent organic group independently, and * indicates a group related to L in formula (R-1). 1 The bonding sites.

[1007] The preferred embodiment of the resin of the present invention is the same as the preferred embodiment of the specific resin described above.

[1008] In particular, it is preferred that the content of free radical polymerizable groups in the resin of the present invention is 0.5 mmol / g or more.

[1009] Furthermore, the resin of the present invention preferably contains the structure represented by formula (2-1) or formula (2-2) above.

[1010] Example

[1011] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are used as mass standards.

[1012] <Synthesis example>

[1013] Synthesis of diamine (DA-1)

[1014] In a flask equipped with a condenser and a stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Corporation), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation), 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.03 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed out, along with 200 mL of isopropanol (IPA) and 30 mL of pure water, and the mixture was stirred.

[1015] Next, 16.2 g of dinitrocellulose (DN-1), obtained by the following synthesis method, was added in a small amount over 1 hour, and the mixture was stirred for 30 minutes. The external temperature was then raised to 85°C, stirred for 2 hours, and cooled to below 25°C. The mixture was then filtered using diatomaceous earth (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel, washed twice with 300 mL of saturated sodium bicarbonate solution, and then successively washed with 300 mL of water and 300 mL of saturated saline solution. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and dried under vacuum to obtain 11.0 g of diamine (DA-1). 1 H-NMR spectroscopy confirmed that it was a diamine (DA-1).

[1016] [Chemical Formula 80]

[1017]

[1018] [Synthesis of BA-1]

[1019] In a round-bottom flask equipped with a thermometer and a calcium chloride tube, 5.00 g (19.2 mmol) of 4,4''-diamino-p-phenyl was dissolved in 40 g of dimethylformamide. Then, 8.60 g (39.4 mmol) of tert-butyl dicarbonate was added, and the mixture was stirred at 60 °C for 3 hours. The reaction solution was crystallized in 500 mL of acetone, the precipitate was filtered and recovered, and dried at 40 °C for 24 hours to obtain 5.9 g of the target compound (BA-1).

[1020] The structure of BA-1 is shown below. According to... 1 H-NMR spectroscopy confirmed the following structure.

[1021] [Chemical Formula 81]

[1022]

[1023] [Synthesis of BA-2 to BA-3]

[1024] With appropriate changes to the raw materials used, BA-2 to BA-3 were synthesized using the same method as BA-1. The structures of BA-2 to BA-3 are shown below. According to... 1 H-NMR spectroscopy confirmed the following structure.

[1025] [Chemical Formula 82]

[1026]

[1027] <Synthesis of BC-1>

[1028] 6.20 g (20 mmol) of 4,4'-oxyphthalic anhydride, 4.93 g (41 mmol) of diethylene glycol monomethyl ether, 3.16 g (40 mmol) of pyridine, and 44.5 g of tetrahydrofuran were weighed into a flask and stirred at 60 °C for 4 hours, then cooled to 25 °C. The reaction mixture was then transferred to a separatory funnel, diluted with 500 mL of ethyl acetate, washed twice with 300 mL of 1N hydrochloric acid solution, 200 mL of water, and 300 mL of saturated saline solution, and dried over sodium sulfate. The organic layer was then transferred to a round-bottom flask and the solvent was removed using an evaporator, yielding 10 g of BC-1 (a mixture of isomers).

[1029] according to 1 1H-NMR spectroscopy confirmed that BC-1 is a compound with the structure represented by the formula BC-1. BC-1 is a mixture of isomers of the following structure.

[1030] [Chemical Formula 83]

[1031]

[1032] Synthesis of dinitro group A-1 containing vinylphenyl group

[1033] In a flask equipped with a stirrer, condenser, and thermometer, 23.06 g (100 mmol) of 3,5-dinitrobenzyl chloride, 0.005 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical, and 9.50 g (120 mmol) of dehydrated pyridine were dissolved in 80 g of dehydrated tetrahydrofuran and cooled to 0–10 °C. Next, 11.92 g (100 mmol) of 4-aminostyrene was dissolved in 40 g of dehydrated tetrahydrofuran and added dropwise over 1 hour at 0–10 °C with stirring. The mixture was then heated to 20–25 °C and stirred for another 2 hours. The above reaction solution was crystallized in 1 L of water and filtered. It was then slurried twice with 500 mL of 0.1 N (mol / L) hydrochloric acid water, rinsed with 500 mL of water, and dried at 40 °C for 24 hours to obtain 30.0 g of dinitrocellulose A-1 with vinylphenyl.

[1034] pass 1 H-NMR spectroscopy confirmed that the structure of A-1 is the structure represented by the following formula (A-1).

[1035] [Chemical Formula 84]

[1036]

[1037] Synthesis of dinitro groups A-2 to A-9 containing vinylphenyl groups

[1038] The raw materials used were appropriately modified, and A-2 to A-9 were synthesized using the same method as A-1. 1 H-NMR spectroscopy confirmed that the structures of A-2 to A-9 are represented by the following formulas (A-2) to (A-9).

[1039] [Chemical Formula 85]

[1040]

[1041] Synthesis of diamine compound AA-1 containing vinylphenyl group

[1042] In a flask equipped with a stirrer, condenser, and thermometer, 5.75 g (95.8 mmol) of acetic acid, 11.3 g (210 mmol) of ammonium chloride, 0.01 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical, 240 mL of isopropanol, and 60 g of water were added. Next, 55.7 g (958 mmol) of reduced iron was added, followed by a small amount of 30.0 g (95.8 mmol) of A-1 synthesized above, added over 1 hour. After stirring for 30 minutes, the mixture was heated to 80°C and stirred for 4 hours. The solution was filtered through a Nutche container lined with diatomaceous earth, and the filtrate was recovered. Next, the filtrate was transferred to a separatory funnel, diluted in 500 mL of ethyl acetate, washed three times with 300 mL of saturated sodium bicarbonate solution, washed once with 300 mL of saturated saline solution, dried with sodium sulfate, the solvent was removed by evaporation, and the precipitated solid was dried at 40 °C for 24 hours to obtain 22 g of diamine compound AA-1 with vinylphenyl group.

[1043] pass 1 H-NMR spectroscopy confirmed that the structure of AA-1 is the structure represented by the following formula (AA-1).

[1044] 1 H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6)

[1045] 5.10 (s, 4H), 5.26~5.29 (d, 1H), 5.81~5.85 (d, 1H), 6.10 (s, 1H),

[1046] 6.58 (s, 2H), 6.72~6.80 (q, 1H), 7.16~7.19 (d, 2H), 7.53~7.55 (d, 2H)

[1047] [Chemical Formula 86]

[1048]

[1049] Synthesis of diamine compounds AA-2 to AA-9 containing vinylphenyl groups

[1050] AA-2 to AA-9 were synthesized using the same method as the diamine compound AA-1 containing a vinylphenyl group, except that any one of A-2 to A-9 was used to replace A-1. 1 H-NMR spectroscopy confirmed that the structures of AA-2 to AA-9 are represented by the following formulas (AA-2) to (AA-9).

[1051] [Chemical Formula 87]

[1052]

[1053] Synthesis of AAA-1 dianhydride containing vinylphenyl group

[1054] In a flask equipped with a stirrer, condenser, and thermometer, 17.3 g (82 mmol) of trimellitic anhydride chloride, 0.005 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical, and 6.96 g (88 mmol) of dehydrated pyridine were dissolved in 80 g of dehydrated tetrahydrofuran and cooled to -10°C to 0°C. Next, 10.17 g (40 mmol) of AA-1 synthesized above was dissolved in 50 g of dehydrated tetrahydrofuran and added dropwise over 2 hours at -10°C to 0°C with stirring for 1 hour. The temperature was then raised to 20°C to 25°C and stirred further for 2 hours. The above reaction solution was transferred to a separatory funnel and dissolved in 1 L of ethyl acetate. The solution was washed twice each with 300 mL of water, 200 mL of 0.5 N hydrochloric acid, 300 mL of saturated sodium bicarbonate solution, and 300 mL of saturated saline solution. The solution was dried with sodium sulfate and the solvent was removed using an evaporator to obtain crude crystals. Next, the crude crystals were mixed with 100 mL of acetic anhydride and stirred at 80 °C for 3 hours. The mixture was then filtered, washed with 300 mL of hexane, and dried at 40 °C for 24 hours to obtain 18.5 g of dianhydride AAA-1 containing vinylphenyl groups.

[1055] pass 1 H-NMR spectroscopy confirmed that the structure of AAA-1 is the structure represented by the following formula (AAA-1).

[1056] [Chemical Formula 88]

[1057]

[1058] Synthesis of dianhydrides AAA-2 to AAA-9 containing vinylphenyl groups

[1059] AAA-2 to AAA-9 were synthesized using the same method as described above for the vinylphenyl dianhydride AAA-1, except that any one of AA-2 to AA-9 was used to replace AA-1. The structures of AAA-2 to AAA-9 are shown below. According to... 1 H-NMR spectroscopy confirmed the following structure.

[1060] [Chemical Formula 89]

[1061]

[1062] [Chemical Formula 90]

[1063]

[1064] [Synthetic Example MA-1: Synthesis of End-Capping Agent (MA-1)]

[1065] 23.02 g (100 mmol) of 4-amino-4'-nitrodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 mL of dimethylformamide were mixed in a flask. Under ice-cooling, 22.91 g (105 mmol) of di-tert-butyl dicarbonate (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise. After the addition was complete, the mixture was stirred at 60 °C for 5 hours. After the reaction was complete, the mixture was cooled to room temperature, diluted in 800 mL of ethyl acetate, and transferred to a separatory funnel. The solution was then washed three times with 300 mL of saturated sodium bicarbonate solution and once with 300 mL of saturated brine, dried over 100 g of sodium sulfate, the solvent was removed using an evaporator, and the mixture was dried under vacuum at 45 °C for 24 hours to obtain 27.2 g of MA-1. 1 H-NMR confirmed that MA-1 has the following structure.

[1066] [Chemical Formula 91]

[1067]

[1068] [Synthetic Example MB-1: Synthesis of Capping Agent (MB-1)]

[1069] 240 mL of isopropanol, 60 mL of pure water, 11.27 g of ammonium chloride, 5.75 g of acetic acid, and 55.7 g of reduced iron were mixed in a flask and stirred within the range of 20°C–30°C. Next, 25 g of MA-1 synthesized above was added, and the mixture was stirred for 1 hour. The temperature was then raised to 80°C, and the mixture was stirred for 4 hours. The mixture was filtered through a Nutche filter lined with diatomaceous earth, and the filtrate was dissolved in 800 mL of ethyl acetate. The solution was transferred to a separatory funnel, washed three times with 300 mL of saturated sodium bicarbonate solution, and once with 300 mL of saturated saline solution. The solution was then dried with 100 g of sodium sulfate, the solvent was removed using an evaporator, and the solution was vacuum dried at 45°C for 24 hours to obtain 20.1 g of MB-1. 1 H-NMR confirmed that MB-1 has the following structure.

[1070] [Chemical Formula 92]

[1071]

[1072] [Synthetic Example SA-1: Synthesis of Polyamic Acid (SA-1)]

[1073] In a flask equipped with a stirrer, condenser, and thermometer, while removing moisture, 6.54 g (30.0 mmol) of pyromellitic anhydride, 10.41 g (20.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 48.74 g of N-methylpyrrolidone (NMP). Next, 7.63 g (30 mmol) of AA-1 (the above-mentioned synthesized product) and 6.40 g (20 mmol) of TFMB (2,2'-bis(trifluoromethyl)benzidine, manufactured by WAKAYAMA SEIKA KOGYO CO.,LTD.) were dissolved in 40 g of N-methylpyrrolidone (NMP). The solution was added dropwise over 1 hour, and the mixture was stirred for 4 hours at 20°C–25°C to obtain a 25% by mass NMP solution of SA-1. 1 H-NMR spectroscopy confirmed that the structure of SA-1 is represented by the following formula (SA-1). In the following structures, the subscripts in parentheses indicate the molar ratio of each structure. SA-1 has a weight-average molecular weight of 16,400, a number-average molecular weight of 7,000, a polymerizability of 0.86 mmol / g, and an imidization rate of 5%.

[1074] [Chemical Formula 93]

[1075]

[1076] Synthesis of polyamic acids SA-2 to SA-6

[1077] The raw materials used were appropriately modified, and SA-2 to SA-6 were synthesized using the same method as SA-1. 1 1H-NMR spectroscopy confirmed that the structures of SA-2 to SA-6 are represented by the following formulas (SA-2) to (SA-6). In the following structures, the subscripts in parentheses indicate the molar ratio of each structure. The weight-average molecular weight (Mw), number-average molecular weight (Mn), polymerizability (mmol / g), and imidization rate (%) of SA-2 to SA-6 are listed in the table below.

[1078] [Chemical Formula 94]

[1079]

[1080] [Chemical Formula 95]

[1081]

[1082] [Chemical Formula 96]

[1083]

[1084] [Chemical Formula 97]

[1085]

[1086] [Table 1]

[1087]

[1088] Synthesis of polyamic acid SA-7 to SA-8

[1089] Using 4-aminophthalic acid and MB-1 synthesized above as end-capping agents, SA-7 to SA-8 were synthesized by the same method as SA-1. 1 ¹H-NMR spectroscopy confirmed that the structures of SA-7 to SA-8 are represented by the following formulas (SA-7) to (SA-8). In the following structures, the subscripts in parentheses indicate the molar ratio of each structure. The weight-average molecular weight (Mw), number-average molecular weight (Mn), polymerizability (mmol / g), and imidization rate (%) of SA-7 to SA-8 are listed in the table below.

[1090] [Chemical Formula 98]

[1091]

[1092] [Table 2]

[1093]

[1094] [Synthetic Example SA-9: Synthesis of Polyamic Acid (SA-9)]

[1095] In a flask equipped with a stirrer, condenser, and thermometer, while removing moisture, 16.58 g (20 mmol) of the acid anhydride AAA-5 synthesized above, 11.37 g (20 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride, 0.10 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical, 3.92 g (84 mmol) of ethanol, 26.58 g (336 mmol) of pyridine, and 100 mL of dimethyl diethylene glycol ether were added, and the mixture was stirred at 60 °C for 6 hours. Next, the reaction solution was cooled to -10 °C to 0 °C, and a solution of 19.3 g (162 mmol) of thionyl chloride and 30 g of dimethyl diethylene glycol ether was added dropwise over 2 hours, followed by stirring for 1 hour after each addition. Next, 11.84 g (35.2 mmol) of TFMB (manufactured by WAKAYAMA SEIKA KOGYO CO.,LTD.) was dissolved in 100 g of NMP and added dropwise over 3 hours at -5°C to 0°C, followed by stirring for another 2 hours. Then, 10 mL of ethanol was added, and the mixture was stirred for 1 hour at 10°C to 20°C. The solution was then diluted with 100 g of acetonitrile, and the reaction mixture was added dropwise to 4 L of water. After stirring for 15 minutes, the polyamic acid resin was filtered and dried under reduced pressure at 45°C for 24 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyamic acid resin was precipitated in 5 L of water and stirred for 15 minutes. The above resin was obtained by filtration and dried at 45°C for 1 day under reduced pressure to obtain polyamic acid (SA-9). The obtained polyimide (SA-9) has a weight-average molecular weight of 20,800 and a number-average molecular weight of 8,600. Polyamic acid (SA-9) is a resin having repeating units represented by the following formula (SA-9). 1 H-NMR spectroscopy determined the structure of the repeating units. In the structures described below, the subscripts in parentheses indicating repeating units indicate the molar ratio of each repeating unit. The polymerizability value is 0.90 mmol / g, and the imidization rate is 3%. The weight-average molecular weight (Mw), number-average molecular weight (Mn), polymerizability value (mmol / g), and imidization rate (%) of SA-9 are listed in the table below.

[1096] [Chemical Formula 99]

[1097]

[1098] [Synthetic Example SA-10: Synthesis of Polyamic Acid (SA-10)]

[1099] In a flask equipped with a stirrer, condenser, and thermometer, while removing moisture, 13.69 g (40 mmol), 0.10 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical, 3.92 g (84 mmol) of ethanol, 26.58 g (336 mmol) of pyridine, and 80 mL of dimethyl diethyl ether were added, and the mixture was stirred at 60 °C for 6 hours. Next, the reaction solution was cooled to -10 °C to 0 °C, and a solution of 19.3 g (162 mmol) of thionyl chloride and 30 mL of dimethyl diethyl ether was added dropwise over 2 hours, followed by stirring for 1 hour after each addition. Next, 9.92 g (27.0 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.95 g (9 mmol) of HAB (manufactured by WAKAYAMA SEIKA KOGYO CO.,LTD.) were dissolved in 70 g of NMP and added dropwise over 3 hours at a temperature of -5°C to 0°C, followed by stirring for 2 hours. Then, 4.97 g (21.6 mmol) of M-1 (the above-mentioned synthesized product) was added, and the mixture was stirred at 45°C for 8 hours. The mixture was then diluted with 80 g of acetonitrile, and the reaction solution was added dropwise to 4 L of water. After stirring for 15 minutes, the polyamic acid resin was filtered and dried under reduced pressure at 45°C for 24 hours. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyamic acid resin was precipitated in 5L of water and stirred for 15 minutes. The resin was then obtained by filtration and dried at 45°C under reduced pressure for 1 day to obtain polyamic acid (SA-10). The obtained polyimide (SA-10) had a weight-average molecular weight of 22,500 and a number-average molecular weight of 8,800. Polyamic acid resin (SA-10) is a resin having repeating units represented by the following formula (SA-10). 1 H-NMR spectroscopy determined the structure of the repeating unit. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit. The polymerizability value is 0.56 mmol / g, and the imidization rate is 12%.

[1100] The weight-average molecular weight (Mw), number-average molecular weight (Mn), polymerizability (mmol / g), and imidization rate (%) of SA-10 are recorded in the table below.

[1101] [Chemical Formula 100]

[1102]

[1103] [Synthetic Example SA-11: Synthesis of Polyamic Acid (SA-11)]

[1104] SA-11 was synthesized using the same method as SA-10, except that the raw materials used were appropriately modified. Polyamic acid (SA-11) is a resin having repeating units represented by the following formula (SA-11). 1 H-NMR spectroscopy determined the structure of the repeating units. In the structures described below, the subscripts in parentheses indicating repeating units indicate the molar ratio of each repeating unit. The weight-average molecular weight (Mw), number-average molecular weight (Mn), polymerizability (mmol / g), and imidization rate (%) of SA-11 are listed in the table below.

[1105] [Chemical Formula 101]

[1106]

[1107] [Table 3]

[1108]

[1109] [Synthetic Example SP-1: Synthesis of Polyimide (SP-1)]

[1110] In a flask equipped with a stirrer, condenser, and thermometer, while removing moisture, 18.1 g (30 mmol) of the acid anhydride AAA-1 synthesized above and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 70 g of N-methylpyrrolidone (NMP). Next, 9.08 g (24.6 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl was dissolved in 30 g of NMP and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring at 25°C for 2 hours, 9.48 g of pyridine and 7.66 g of acetic anhydride were added, and the reaction was carried out at 80°C for 4 hours. After the reaction was complete, the mixture was cooled to 25°C and diluted with 100 g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 1.2 L of methanol and 0.3 L of water. After stirring for 15 minutes, the polyimide resin was filtered. Then, the resin was re-slurryed with 1 L of water and filtered again, followed by re-slurrying with 1 L of methanol and filtering. The resin was then dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 200 g of tetrahydrofuran, and 30 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (SP-1). The obtained polyimide (SP-1) had a weight-average molecular weight of 17,200 and a number-average molecular weight of 7,600. Polyimide (SP-1) is a resin having repeating units represented by the following formula (SP-1). 1 H-NMR spectroscopy determined the structure of the repeating unit. The imidization rate was 100%.

[1111] [Chemical Formula 102]

[1112]

[1113] [Synthetic Examples SP-2 to SP-5: Synthesis of Polyimides (SP-2) to (SP-5)]

[1114] With appropriate changes to the raw materials used, SP-2 to SP-5 were synthesized using the same method as SP-1. Polyimide (SP-2) to (SP-5) are resins having repeating units represented by the following formulas (SP-2) to (SP-5). 1 H-NMR spectroscopy determined the structure of the repeating units. In the structures described below, the subscripts in parentheses indicating repeating units indicate the molar ratio of each repeating unit. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polyimides (SP-2) to (SP-5) are listed in the table below.

[1115] [Chemical Formula 103]

[1116]

[1117] [Chemical Formula 104]

[1118]

[1119] [Table 4]

[1120]

[1121] [Synthetic Example SP-6: Synthesis of Polyimide (SP-6)]

[1122] 6.05 g (28.5 mmol) of m-toluidine, 12.78 g (28.5 mmol) of AA-1, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 100 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 26.68 g (51.3 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride was dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at 10°C–25°C. After stirring at 25°C for 60 minutes, 1.87 g (8.55 mmol) of di-tert-butyl dicarbonate was added dropwise, and the mixture was stirred at 45°C for 3 hours. Then, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the mixture was reacted at 80°C for 4 hours. After the reaction was completed, the solution was cooled to 25°C and diluted with 200g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 1.5L methanol and 0.5L water, stirred for 15 minutes, and then the polyimide resin was filtered. The resin was then re-slurryed with 1L water for 30 minutes and filtered, followed by re-slurrying with 1L methanol and filtering. The resin was then dried under reduced pressure at 40°C for 10 hours. The dried resin was then dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (SP-6).

[1123] The obtained polyimide (SP-6) has a weight-average molecular weight of 22,500, a number-average molecular weight of 7,200, and an imidization rate of 100%. Polyimide (SP-6) is a resin having repeating units represented by the following formula (SP-6). 1H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1124] [Chemical Formula 105]

[1125]

[1126] <Comparative Synthesis of Compound A-1>

[1127] In a flask equipped with a stirrer, condenser, and thermometer, 41.4 g (114 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 57.29 g (125.0 mmol) of bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene were added while removing moisture, along with 492.43 g of γ-butyrolactone. The mixture was stirred at 60 °C for 1.5 hours. Next, 50 mL of toluene was added, and the temperature was raised to 180 °C while nitrogen was added at a flow rate of 200 mL / min. The mixture was stirred for 3 hours and then cooled to room temperature. The obtained polymerization solution was diluted with acetone to prepare a diluent, which was then added dropwise to a water / methanol mixture of 3 / 1, causing a white solid to precipitate. The obtained white solid was recovered and dried under vacuum at 120 °C to obtain 90 g of polymer.

[1128] Next, 73.86 g (150.0 mmol equivalent of hydroxyl groups), 23.27 g (150.0 mmol) of ethyl 2-isocyanate methacrylate, and 828.3 g of γ-butyrolactone (GBL) were placed in a reaction vessel equipped with a stirrer and a cooling pipe. The temperature was then raised to 120°C while stirring, and the reaction was allowed to proceed for 6 hours. The resulting reaction solution was then diluted with acetone to prepare a diluent, which was then added dropwise to a 2 / 1 water / methanol mixture, causing a white solid to precipitate. The white solid was recovered and vacuum dried at 40°C to obtain 85.8 g of A-1. The weight-average molecular weight (Mw) of A-1 was 32,200, and the number-average molecular weight (Mn) was 12,800. 1 H-NMR spectroscopy confirmed that the structure of A-1 was dominated by the structure represented by the following formula (A-1). 1 According to H-NMR measurements, the cross-linking group incorporation rate was 50%.

[1129] [Chemical Formula 106]

[1130]

[1131] <Comparative Synthesis of Compound A-2>

[1132] 77.5 g of 4,4'-oxyphthalic dianhydride (ODPA) and 73.5 g of 4,4'-biphenyl dianhydride were added to a separating flask, along with 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone. While stirring at room temperature, 79.1 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was cooled to room temperature and allowed to stand for 16 hours.

[1133] Next, under ice-cooled conditions, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Then, a suspension of 96.0 g of 4,4'-diaminodiphenyl ether suspended in 350 mL of γ-butyrolactone was added over 60 minutes with stirring. After stirring at room temperature for 2 hours, 30 mL of ethanol was added, and stirring continued for 1 hour. Finally, 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration, thus yielding the reaction solution.

[1134] The obtained reaction solution was added to 3 L of ethanol, thereby generating a precipitate composed of crude polymer. The generated crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran, thereby obtaining a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to obtain powdered polymer A-2. A-2 has a weight-average molecular weight of 32,100 and a number-average molecular weight of 12,500. A-2 is a resin having repeating units represented by the following formula (A-2). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts in parentheses representing repeating units indicate the molar ratio of each repeating unit.

[1135] [Chemical Formula 107]

[1136]

[1137] <Comparative Synthesis of Compound A-3>

[1138] In a flask equipped with a stirrer, condenser, and thermometer, while removing moisture, 12.42 g (40.0 mmol) of 4,4'-oxyphthalic anhydride and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were dissolved in 65.79 g of N-methylpyrrolidone (NMP). Next, 9.51 g (36 mmol) of DA-1 (the above-mentioned synthesized product) and 6.40 g (20 mmol) of TFMB (manufactured by WAKAYAMA SEIKA KOGYO CO.,LTD.) were dissolved in 40 g of N-methylpyrrolidone (NMP). The mixture was added dropwise over 1 hour, and the mixture was stirred for 4 hours at 20°C–25°C to obtain a 25% by weight NMP solution of A-3. A-3 has a weight-average molecular weight of 22,500, a number-average molecular weight of 9,000, a polymerizability of 1.49 mmol / g, and an imidization rate of 5%. A-3 is a resin having repeating units represented by the following formula (A-3). 1 H-NMR spectroscopy determined the structure of the repeating unit.

[1139] [Chemical Formula 108]

[1140]

[1141] <Examples and Comparative Examples>

[1142] In each embodiment, the components listed in the table below were mixed to obtain each resin composition. Furthermore, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition.

[1143] Specifically, the content of each component recorded in the table is set to the amount (parts by mass) recorded in the "Amount Added" column of each column of the table.

[1144] The obtained resin composition and the comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm.

[1145] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[1146] [Table 5]

[1147]

[1148] [Table 6]

[1149]

[1150] The detailed information of each component recorded in the table is as follows.

[1151] [Specific resins]

[1152] •SA-1~SA-11: SA-1~SA-11 synthesized in the above process

[1153] [Other resins]

[1154] SP-1 to SP-6: SP-1 to SP-6 synthesized in the above process

[1155] • A-1 to A-3: The above-mentioned synthetic products (for comparative examples)

[1156] [Polymerizing compounds]

[1157] • B-1: SR-209: SR-209 (manufactured by Sartomer Company, Inc., melting point: below 25°C)

[1158] • B-2: ADPH: Dinepentylenetetraol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: below 25°C)

[1159] • B-3: Tris(2-methacryloyloxyethyl) isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1160] [Solvent]

[1161] DMSO: Dimethyl sulfoxide (boiling point 189℃)

[1162] GBL: γ-Butyrolactone (boiling point 204℃)

[1163] • NMP: N-methylpyrrolidone (boiling point 202℃)

[1164] γ-Velolactone (boiling point 207℃)

[1165] • MDPPA: KJCMPA-100 (manufactured by KJ Chemicals Corporation, boiling point 215°C)

[1166] The entries “DMSO / GBL” and “DMSO / γ-valerol” in the table indicate the use of a mixture obtained by mixing DMSO and GBL at a mass ratio of DMSO:GBL=20:80 and DMSO:γ-valerol=20:80.

[1167] [Polymerization initiator]

[1168] •C-1: IRGACURE OXE 01 (manufactured by BASF)

[1169] •C-2: IRGACURE OXE 02 (manufactured by BASF)

[1170] • C-3: Irgcue 784 (manufactured by BASF)

[1171] • C-4: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1172] 〔additive〕

[1173] ·BA-1~BA-3: BA-1~BA-3 synthesized in the above process

[1174] ·BC-1: BC-1 synthesized in the above process

[1175] [Sensitizer]

[1176] • J-1~J-2: Compounds with the following structures

[1177] [Chemical Formula 109]

[1178]

[1179] [Migration Inhibitor]

[1180] •E-1~E-7: Compounds with the following structures

[1181] [Chemical Formula 110]

[1182]

[1183] [Metal adhesion modifier]

[1184] • F-1~F-3: Compounds with the following structures

[1185] [Chemical Formula 111]

[1186]

[1187] • F-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1188] • F-5: KBM-51073 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1189] • F-6: X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1190] [Polymerization inhibitor]

[1191] G-1: 1,4-Benzoquinone

[1192] G-2: 4-Methoxyphenol

[1193] G-3: 1,4-Dihydroxybenzene

[1194] • G-4: Compounds with the following structures

[1195] [Chemical Formula 112]

[1196]

[1197] [Alkali-producing agent]

[1198] • H-1~H-3: Compounds with the following structures

[1199] [Chemical Formula 113]

[1200]

[1201] [Metal complex]

[1202] • I-1: TC-750 (manufactured by Matsumoto Fine Chemical Co. Ltd.)

[1203] • I-2: TC-401 (manufactured by Matsumoto Fine Chemical Co. Ltd.)

[1204] • I-3: Compounds with the following structures

[1205] [Chemical Formula 114]

[1206]

[1207] <Evaluation>

[1208] [Resolution Evaluation]

[1209] The resin compositions used in each embodiment and comparative example were applied in a layered manner to the surface of a copper thin layer on a resin substrate having a copper thin layer formed thereon using a spin coating method. After drying at 100°C for 5 minutes to form a resin composition layer with a film thickness of 5 μm, a stepper (FPA-3000 i5 (manufactured by Canon Inc.)) was used with NA=0.50 and 300 mJ / cm². 2Exposure was performed. For exposure, a mask with a hole pattern pattern of 3–20 μm diameter formed at 1 μm scales was used at a wavelength of 365 nm. Next, development was performed for 15 seconds with the developer listed in the "Developer" column of the table, followed by rinsing with PGMEA for 30 seconds. Further heating was carried out under a nitrogen atmosphere at a rate of 10 °C / min, and the process was repeated at the temperature and time listed in the "Curing Conditions" column of the table to obtain a hole pattern of 3–20 μm. The formed hole pattern was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Resolution" column of the table. Image analysis using SEM (Scanning Electron Microscopy) was performed, and analysis was considered possible if the residual film at the bottom of the hole was less than 1%. Generally speaking, the smaller the diameter of the hole pattern, the better the resolution; for example, A, B, or C are preferred.

[1210] -Evaluation Criteria-

[1211] A: It can analyze hole patterns up to 3μm in diameter.

[1212] B: It can analyze hole patterns with a diameter of 5μm, but cannot analyze hole patterns with a diameter of 3μm.

[1213] C: It can analyze hole patterns with a diameter of 7μm, but cannot analyze hole patterns with a diameter of 5μm.

[1214] D: It can analyze hole patterns with a diameter of 10μm, but cannot analyze hole patterns with a diameter of 7μm.

[1215] E: Unable to analyze hole patterns with a diameter of 10μm.

[1216] [Evaluation of elongation at break]

[1217] In each embodiment and comparative example, the resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer with the obtained resin composition layer applied was dried at 100°C for 5 minutes on a hot plate to obtain a uniform resin composition layer with a thickness of approximately 15 μm on the silicon wafer.

[1218] Using a stepper motor (Nikon NSR 2005 i9C), at 500 mJ / cm 2 The entire surface of the obtained resin composition layer was exposed to i-rays using an exposure energy of [energy value missing].

[1219] The exposed resin composition layer (resin layer) was heated under a nitrogen atmosphere at a rate of 10°C / min. After reaching the temperature recorded in the "Temperature" column of the "Curing Conditions" section of the table, it was heated at that temperature for the time recorded in the "Time" column of the "Curing Conditions" section of the table. The cured resin layer (cured film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution and then peeled off from the silicon wafer. The peeled-off cured film was punched using a punching machine to produce test pieces with a sample width of 3 mm and a sample length of 30 mm. Regarding the obtained test pieces, the elongation at break in the longitudinal direction of the test pieces was determined according to JIS-K6251 using a tensile testing machine (manufactured by Tensilon, A&D Company, Limited) at a crosshead speed of 300 mm / min at 25°C and 65% RH (relative humidity). Five evaluations were performed, and the arithmetic mean of the elongation at break (elongation at break) of the test pieces was used as the index value.

[1220] Evaluate the above index values ​​according to the evaluation criteria below, and record the evaluation results in the "Elongation at Break" column of the table. It can be said that the higher the above index value, the better the film strength (elongation at break) of the obtained cured film.

[1221] (Evaluation Criteria)

[1222] A: The above indicator value is above 60%.

[1223] B: The above indicator value is above 50% and less than 60%.

[1224] C: The above indicator value is above 40% and less than 50%.

[1225] D: The above indicator value is less than 40%.

[1226] [Evaluation of the coefficient of linear thermal expansion (CTE)]

[1227] In each embodiment and comparative example, the resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer with the obtained resin composition layer applied was dried at 100°C for 5 minutes on a hot plate to obtain a uniform resin composition layer with a thickness of approximately 15 μm on the silicon wafer.

[1228] Using a stepper motor (Nikon NSR 2005 i9C), at 500 mJ / cm 2 The entire surface of the obtained resin composition layer was exposed to i-rays using an exposure energy of [energy value missing].

[1229] The exposed resin composition layer (resin layer) was heated under a nitrogen atmosphere at a rate of 10°C / min. After reaching the temperature recorded in the "Temperature" column of the "Curing Conditions" section of the table, it was heated at that temperature for the time recorded in the "Time" column of the "Curing Conditions" section of the table. The cured resin layer (cured film) was immersed in a 4.9% (w / w) hydrofluoric acid aqueous solution and then peeled off from the silicon wafer. The peeled-off cured film was punched using a punching machine to produce test pieces with a sample width of 3 mm and a sample length of 30 mm.

[1230] For the above-mentioned test pieces (cured products), the elongation (displacement) was measured while the temperature was changed using the Discovery TMA thermomechanical analysis / coefficient of thermal expansion device manufactured by TA Instruments Japan Inc.

[1231] The heating and cooling conditions during the evaluation are set as follows (1) to (4).

[1232] (1) Heat from room temperature to 130°C at a heating rate of 5°C / minute.

[1233] (2) Cool down from 130℃ to 10℃ at a cooling rate of 5℃ / minute.

[1234] (3) Heat from 10℃ to 220℃ at a heating rate of 5℃ / minute.

[1235] (4) Allow to cool naturally to room temperature.

[1236] During the heating and cooling processes of (1) to (4) above, the elongation (displacement) of the sample was measured, and the elongation (displacement) of the sample at 25℃ and 125℃ in process (3) was calculated by dividing the temperature difference and used as the coefficient of thermal expansion.

[1237] (Example: If the length of the sample at 25℃ is 30mm and the length of the sample at 125℃ is 30.12mm, the displacement is calculated to be 0.4% = 4000ppm, and the coefficient of thermal expansion is calculated to be 4000 / (125-25) = 40ppm / K.)

[1238] The obtained coefficient of thermal expansion is evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "CTE" column of the table.

[1239] (Evaluation Criteria)

[1240] A: CTE is below 35 ppm / K.

[1241] B: CTE exceeds 35 ppm / K but is below 50 ppm / K.

[1242] C: CTE exceeds 50 ppm / K but is below 65 ppm / K.

[1243] D: CTE exceeds 65ppm / K.

[1244] [Evaluation of curing shrinkage]

[1245] In each embodiment and comparative example, the resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer with the obtained resin composition layer applied was dried at 100°C for 5 minutes on a hot plate to obtain a uniform curable resin composition layer with a thickness of approximately 15 μm on the silicon wafer. The film thickness of the curable resin composition layer was measured using a reflectance film thickness meter (manufactured by FE-3000 OTSUKA ELECTRONICS CO.,LTD), and this value is designated as "film thickness A".

[1246] Next, using a stepper motor (Nikon NSR 2005 i9C) at 500mJ / cm 2 The entire surface of the obtained curable resin composition layer was exposed to i-rays using an exposure energy of [energy value missing].

[1247] The exposed curable resin composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 10°C / min. After reaching the temperature recorded in the "Temperature" column of the table under "Curing Conditions", the layer was heated at that temperature for the time recorded in the "Time" column of the table under "Curing Conditions", and then cooled to 25°C to obtain a cured product.

[1248] The film thickness of the cured material was measured using a reflectance film thickness meter (manufactured by FE-3000 OTSUKA ELECTRONICS CO.,LTD) and this value was designated as "film thickness B".

[1249] Calculate the membrane shrinkage rate using the following formula.

[1250] Calculation formula: Shrinkage rate (%) = 100 - (film thickness B ÷ film thickness A × 100)

[1251] The evaluation was conducted according to the following criteria, and the results are recorded in the "Cure Shrinkage" column of the table. The smaller the shrinkage rate value, the better the cure shrinkage of the obtained composite layer.

[1252] (Evaluation Criteria)

[1253] A: The membrane shrinkage rate is less than 10%.

[1254] B: The membrane shrinkage rate is greater than 10% and less than 20%.

[1255] C: The membrane shrinkage rate is greater than 20% and less than 30%.

[1256] D: The membrane shrinkage rate is over 30%.

[1257] [Evaluation of Insulation Reliability]

[1258] The resin compositions or comparative compositions prepared in each example and comparative example were applied in layers onto a copper substrate using a spin coating method, thereby forming a resin composition layer or a comparative composition layer. The copper substrate with the obtained resin composition layer or comparative composition layer was dried at 100°C for 5 minutes on a hot plate, thereby forming a resin composition layer or comparative composition layer with a uniform thickness of 5 μm on the copper substrate. Using a stepper (Nikon NSR 2005 i9C) and a photomask with a 100 μm square non-mask portion, i-rays were passed through the substrate at 500 mJ / cm². 2 The resin composition layer or comparative composition layer on the copper substrate is exposed to the specified exposure energy, then developed for 60 seconds with the developer listed in the "Developer" column of the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a 100 μm square resin layer. Then, under a nitrogen atmosphere, at the temperature listed in the "Temperature" column of the table's "Curing Conditions" section, and for the time listed in the "Time" column of the table's "Curing Conditions" section, a heated oven is used to form the resin layer (pattern).

[1259] After the resin layer and copper substrate were subjected to a constant temperature bath at 175°C for 1000 hours, cross-sectional SEM (scanning microscope) measurements were performed, and the porosity between the copper substrate and the resin layer was evaluated. The porosity was calculated using the following formula.

[1260] Porosity (%) = (Area of ​​voids observed by SEM) / (Total area of ​​resin layer) × 100

[1261] Based on the obtained void area ratio, the following evaluation criteria were used. The evaluation results are recorded in the "Insulation Reliability" column of the table. It can be said that the smaller the void area ratio, the better the reliability of the cured film after the HTS (High Temperature Storage-test), and even after a long period of time, voids are less likely to form between the metal layer and the cured material, indicating good insulation reliability.

[1262] -Evaluation Criteria-

[1263] A: The void area ratio is less than 0.1%.

[1264] B: The void area ratio is greater than 0.1% and less than 0.3%.

[1265] C: The void area ratio is greater than 0.3% and less than 0.5%.

[1266] D: The porosity exceeds 0.5%.

[1267] Based on the above results, it can be seen that the resin composition of the present invention can produce cured products with a small coefficient of thermal expansion and high resolution. In contrast, it can be seen that the cured products obtained from the compositions of Comparative Examples 1 to 3, which do not contain the specified resin, have a large coefficient of thermal expansion and low resolution.

[1268] <Example 101>

[1269] The resin composition used in Example 1 was applied in a layered manner to the surface of a copper layer on a resin substrate having a copper layer formed thereon by spin coating. After drying at 100°C for 4 minutes to form a resin composition layer with a thickness of 20 μm, exposure was performed using a stepper (manufactured by Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-to-space pattern and a linewidth of 10 μm). After exposure, the layer was heated at 100°C for 4 minutes. Following the heating, the layer was developed in cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern.

[1270] Next, the temperature was increased at a rate of 10°C / min under a nitrogen atmosphere, and after reaching 230°C, it was maintained at 230°C for 3 hours, thereby forming an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer has excellent insulation properties.

[1271] Furthermore, semiconductor devices were fabricated using these rewiring layers with interlayer insulating films, and as a result, they were confirmed to operate without any problems.

Claims

1. A resin composition comprising: Polyamic acid, having at least one of the structures selected from the group consisting of the structure represented by formula (P-1) and the structure represented by formula (P-2); and Photoradical polymerization initiator In equation (P-1), R P1 This indicates a monovalent organic group, n represents an integer from 0 to 4, and * indicates a bonding site with other structures. In equation (P-2), R P2 Each symbol represents a hydrogen atom or a monovalent organic group independently, and * indicates a bonding site with other structures.

2. The resin composition according to claim 1, wherein, The polyamic acid comprises repeating units represented by the following formula (1-1), In equation (1-1), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 3 and R 4 Let each of the following expressions (R-1) represent the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1. In equation (R-1), L 1 A represents a linker base with valence a1+1. 1 This represents the structure indicated by equation (P-1) or equation (P-2), where a1 represents an integer greater than or equal to 1, and * represents the structure related to X in equation (1-1). 2 Or Y 2 The bonding sites.

3. The resin composition according to claim 2, wherein, The polyamic acid comprises a structure represented by formula (2-1) or formula (2-2) below. In equations (2-1) and (2-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 Each independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, V 1 Z represents a linker base that is either a single bond or divalent. 1 Q represents the optional protected amino group. 1 R represents a structure containing an optionally protected carboxyl group. 3 R 4 Each of the above expressions independently represents the structure represented by the formula (R-1), where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

4. The resin composition according to any one of claims 1 to 3, further comprising a resin different from the polyamic acid and comprising repeating units represented by the following formula (3-1), In equation (3-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Let each of the following expressions (R-2) represent the structure independently, where m represents an integer from 0 to 4, and n represents an integer greater than or equal to 1. In equation (R-2), L 2 A represents a linker basis with a valence of a²+1. 2 The symbol represents a polymerizable group, a2 represents an integer greater than or equal to 1, and * represents X in equation (3-1). 1 Or Y 1 The bonding sites.

5. The resin composition according to claim 4, wherein, A in equation (R-2) included in equation (3-1) 2 At least one of them is vinylphenyl, (meth)acryloyloxy, vinyl ether, maleimide, allyl or a group containing these.

6. The resin composition according to claim 4, wherein, In equation (3-1), A in equation (R-2) 2 At least one of them is vinylphenyl.

7. The resin composition according to any one of claims 1 to 3, further comprising a polymerizable compound.

8. The curable resin composition according to any one of claims 1 to 3, further comprising an azole compound and a silane coupling agent.

9. The resin composition according to any one of claims 1 to 3, comprising a solvent having a boiling point of 100°C to 260°C.

10. The resin composition according to claim 9, wherein, The content of the solvent with a boiling point of 100°C to 260°C is 40% by mass or more relative to the total mass of the composition.

11. The resin composition according to claim 9, comprising two or more solvents having a boiling point of 100°C to 260°C.

12. The resin composition according to any one of claims 1 to 3, used for forming an interlayer insulating film for a rewiring layer.

13. A cured product formed by curing the resin composition according to any one of claims 1 to 3.

14. A laminate comprising two or more layers formed of the cured material of claim 13, and comprising a metal layer between any of the layers formed of the cured material.

15. A method for manufacturing a cured product, the method comprising a film forming step of applying the resin composition of any one of claims 1 to 3 onto a substrate to form a film.

16. The method for manufacturing a cured material according to claim 15, the method 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.

17. The method for manufacturing a cured material according to claim 15, the method comprising a heating step of heating the film at 50°C to 450°C.

18. A method for manufacturing a laminate, the method comprising the method for manufacturing a cured material as described in claim 15.

19. A method for manufacturing a semiconductor device, the method comprising the method for manufacturing a cured material as described in claim 15.

20. A semiconductor device comprising the cured material of claim 13.

21. A resin comprising repeating units represented by the following formula (1-1), In equation (1-1), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 3 and R 4 Let each of the following expressions (R-1) represent the structure independently, where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1. In equation (R-1), L 1 A represents a linker base with valence a1+1. 1 The structure represented by equation (P-1) or (P-2) is given, where a1 represents an integer greater than 1, and * represents the structure related to X in equation (1-1). 1 Or Y 1 The bonding site, In equation (P-1), R P1 The symbol represents a monovalent organic group, n represents an integer from 0 to 4, and * represents the L in formula (R-1). 1 The bonding site, In equation (P-2), R P2 Each of the above represents a hydrogen atom or a monovalent organic group independently, and * indicates a group related to L in formula (R-1). 1 The bonding sites.

22. The resin according to claim 21, wherein, The resin has a free radical polymerizable group content of 0.5 mmol / g or more.

23. The resin according to claim 21 or 22, wherein, The resin comprises the structure represented by (2-1) or (2-2) below. In equations (2-1) and (2-2), X 2 Y represents an organic group with 4 or more carbon atoms. 2 R represents an organic group with 4 or more carbon atoms. 1 and R 2 Each independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, V 1 Z represents a linker base that is either a single bond or divalent. 1 Q represents the optional protected amino group. 1 R represents a structure containing an optionally protected carboxyl group. 3 R 4 Each of the above expressions independently represents the structure represented by the formula (R-1), where m represents an integer from 0 to 4, n represents an integer from 0 to 4, and the sum of m and n is an integer greater than or equal to 1.

Images