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

Abstract

The present application provides a resin composition, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product, the resin composition including resin A and a photosensitizer B, wherein the resin A includes an amic acid ester structure and an amic acid structure, and further includes at least one structure selected from the group consisting of a structure represented by formula (AY1) and a structure represented by formula (DY1), the mole amount of the amic acid ester structure in the resin A is 90.00-99.90% relative to the total mole amount of the amic acid structure and the amic acid ester structure, and the amine value of the resin A is 0.0010-0.3000 mmol / g.

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, and a semiconductor device. Background Technology

[0002] Today, resin materials made from resin compositions containing resins are being used in a wide variety of fields.

[0003] For example, cyclized resins such as polyimide have excellent heat resistance and insulation properties, and are therefore used in a variety of applications. These applications are not particularly limited; for example, in mounting semiconductor devices, they can be used as insulating films, end-capping 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, cyclized resins such as polyimide are used in the form of a resin composition comprising the cyclized resin or its precursor.

[0005] This resin composition is applied to a substrate, for example, by coating, to form a photosensitive film. Then, exposure, development, heating, etc., are performed as needed, thereby forming a cured product on the substrate.

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability. For example, the shape, size, and application location of the resin composition can be designed with a high degree of freedom. From this perspective of excellent manufacturing adaptability, in addition to the high performance of cyclized resins such as polyimide, there is growing anticipation for the industrial application development of the aforementioned resin composition.

[0007] For example, Patent Document 1 describes a photosensitive resin composition containing: a polyimide precursor having a weight-average molecular weight of 40,000 or more and having polymerizable unsaturated bonds; a polymerizable monomer; a photopolymerization initiator; and a solvent.

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2022-21936 Summary of the Invention

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

[0012] In recent years, in the context of the increasing demand for high dimensional uniformity in redistribution layer (RDL) insulating films used in semiconductor packaging, the linewidth uniformity within the wafer plane has become a challenge. Specifically, it is required, for example, to have a small linewidth difference between the outer periphery and the center of the wafer.

[0013] The present invention aims to provide a resin composition capable of forming a patterned curing layer with high linewidth uniformity in a wafer plane, a cured product formed 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.

[0014] means for solving technical problems

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

[0016] <1> A resin composition comprising resin A and photosensitizer B, wherein,

[0017] Resin A comprises an amide ester structure and an amide acid structure, and further comprises at least one structure selected from the group consisting of the structure represented by formula (AY1) and the structure represented by formula (DY1).

[0018] The molar amount of the above-mentioned amyl ester structure in resin A is 90.00% to 99.90% relative to the total molar amount of the above-mentioned amyl acid structure and the above-mentioned amyl ester structure.

[0019] The amine value of resin A is 0.0010–0.3000 mmol / g;

[0020] [Chemical Formula 1]

[0021]

[0022] In the formula,

[0023] * indicates a bonding site with other structures.

[0024] X is the group represented by formula (2a), where *1 to *4 represent the bonding sites with the carbonyl group, respectively.

[0025] [Chemical Formula 2]

[0026]

[0027] Y is any group selected from the following.

[0028] [Chemical Formula 3]

[0029]

[0030] <2> The resin composition according to <1> contains a nitrogen-containing heterocyclic compound.

[0031] <3> The resin composition according to <1> or <2>, wherein,

[0032] The above resin composition comprises the structure represented by formula (1);

[0033] [Chemical Formula 4]

[0034]

[0035] In equation (1), R 1 and R 2 Each of the following groups independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group that can be substituted with an alkyl group having 1 to 10 carbon atoms: X 1 L represents an oxygen atom or a sulfur atom. 1 This represents -C (=O)- or -S (=O)2-, * 1 and* 2 Each independently represents a bonding site with other structures, R 1 R 2 , bonded to * 1 Structure and bonding to * 2 At least two of the structures can bond together to form a ring structure.

[0036] The molar amount of the structure represented by formula (1) relative to the total solids content of the above resin composition is 0.005 to 0.5 mmol / g.

[0037] <4> The resin composition according to any one of <1> to <3>, wherein,

[0038] Resin A includes the structure represented by the formula (1-dp-2d1);

[0039] [Chemical Formula 5]

[0040]

[0041] In the formula, * indicates the bonding site with other structures.

[0042] <5> The resin composition according to <4>, wherein,

[0043] Resin A comprises at least one structure selected from the structure represented by formula (1-dp-V1-1) and the structure represented by formula (Y-V1-1);

[0044] [Chemical Formula 6]

[0045]

[0046] In the formula, * indicates the bonding site with other structures.

[0047] <6> The resin composition according to any one of <1> to <5>, wherein,

[0048] Resin A contains an imide ring structure, and the imidization rate of resin A is 3-40%.

[0049] <7> The resin composition according to any one of <1> to <6>, wherein,

[0050] The weight-average molecular weight of resin A is 15,000 to 40,000.

[0051] <8> The resin composition according to any one of <1> to <7>, wherein,

[0052] The acid values ​​of the acid groups in resin A, whose neutralization point pH ranges from 7.0 to 12.0, range from 0.0010 to 0.3000 mmol / g.

[0053] <9> The resin composition according to any one of <1> to <8> further comprises a titanium complex compound.

[0054] <10> The resin composition according to any one of <1> to <9>, wherein,

[0055] Photosensitive agent B contains an oxime compound.

[0056] <11> The resin composition according to any one of <1> to <10> further comprises an antioxidant.

[0057] <12> The resin composition according to any one of <1> to <11> further comprises an aniline compound.

[0058] <13> The resin composition according to any one of <1> to <12> further comprises a urea compound.

[0059] <14> The resin composition according to any one of <1> to <13> is used to form an interlayer insulating film for a redistribution layer.

[0060] <15> A cured product formed by curing the resin composition described in any one of <1> to <14>.

[0061] <16> A laminate comprising two or more layers made of the cured material described in <15>, wherein a metal layer is included between any of the layers made of the cured material.

[0062] <17> A method for manufacturing a cured material, comprising:

[0063] The film forming process involves applying the resin composition described in any one of <1> to <14> onto a substrate to form a film.

[0064] <18> The method for manufacturing the cured material according to <17> includes an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.

[0065] <19> The method for manufacturing a cured product according to <17> or <18> includes:

[0066] The heating process involves heating the membrane at 50–450°C.

[0067] <20> A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in any one of <17> to <19>.

[0068] <21> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in any one of <17> to <19>.

[0069] <22> A semiconductor device comprising the cured material described in <15>.

[0070] Invention Effects

[0071] According to the present invention, a resin composition capable of forming a patterned curing layer with high linewidth uniformity in a wafer plane is provided, a cured product formed 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. Detailed Implementation

[0072] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0073] In this specification, the numerical range represented by the symbol “~” indicates the range included by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0074] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the expected function of the process can be achieved.

[0075] In the designation of bases (atomic groups) in this specification, the designations without "substituted" or "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).

[0076] 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, and activated light or radiation such as electron beams.

[0077] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either, “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either, and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either.

[0078] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0079] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition. Furthermore, in this specification, solids concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0080] 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) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series 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, unless otherwise specified, the detection used in GPC measurements shall be a UV (ultraviolet) detector with a wavelength of 254 nm.

[0081] 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 in the multilayer of interest. That is, a third layer or element may be further interposed between the reference layer and the other layers, and the reference layer does not need 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 set for ease of explanation of this specification; in practice, the "upper" direction in this specification may differ from vertically upward.

[0082] Unless otherwise specified in this specification, each component in a composition may contain two or more compounds belonging to that component. Unless otherwise specified, the content of each component in the composition represents the total content of all compounds belonging to that component.

[0083] Unless otherwise specified in this manual, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0084] In this specification, the preferred combination of methods is a more preferred method.

[0085] (Resin composition)

[0086] The resin composition of the present invention is a resin composition comprising resin A and photosensitizer B. Resin A comprises an amide ester structure and an amide acid structure, and further comprises at least one structure selected from the group consisting of the structure represented by formula (AY1) and the structure represented by formula (DY1). The molar amount of the amide ester structure in resin A is 90 to 99.9% relative to the total molar amount of the amide acid structure and the amide ester structure. The amine value of resin A is 0.0010 to 0.3000 mmol / g.

[0087] 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.

[0088] The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers.

[0089] Furthermore, the resin composition of the present invention can be used to form a photosensitive film for negative development or a photosensitive film for positive development, but is preferably used to form a photosensitive film for negative development.

[0090] The resin composition of the present invention is preferably used to form a cured product that is at least partially in contact with a metal. Examples of metals include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Examples include copper and aluminum or alloys containing at least one of these metals, preferably copper or alloys containing copper.

[0091] 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.

[0092] As the above-described exposure method, developer, and development method, 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 can be used.

[0093] Using the resin composition of the present invention, a patterned cured layer with high linewidth uniformity within the wafer surface can be formed.

[0094] The mechanism by which these effects are achieved is not yet clear, but the following is a hypothesis.

[0095] To improve linewidth uniformity within the wafer plane, it is inferred that it is important to mitigate the effects of environmental amines caused by exhaust equipment within the manufacturing apparatus and to minimize positional dependence of development. Furthermore, environmental amines refer to ammonia and amines present in the cleanroom of the manufacturing apparatus and within devices or equipment placed within the cleanroom. Examples of amines include methylamine, 2-amino-2-methyl-1-propanol, butylamine, monoethanolamine, and N-methylethanolamine.

[0096] It is inferred that in the resin composition of the present invention, the esterification rate and amine value of the resin are within a specific range, thus buffering the effects of environmental amines and making the composition less susceptible to their influence. Furthermore, the structures represented by formula (AY1) and (DY1) are both small and rigid, and by having this structure as the resin framework, the molecules are easily packed together, and the penetration of environmental amines or developer components into the film is suppressed, thereby reducing the position-dependent effects within the wafer plane.

[0097] Here, in Patent Document 1, neither the resin composition comprising the resin is described nor implied, that the resin comprises at least one structure selected from the group consisting of the structure represented by formula (AY1) and the structure represented by formula (DY1), having an esterification rate of 90 to 99.9% and an amine value of 0.0010 to 0.3000 mmol / g.

[0098] The details of the resin composition of the present invention will be described below.

[0099] <Specific Resin: Resin A>

[0100] Resin A comprises an amide ester structure and an amide acid structure, and further comprises at least one structure selected from the group consisting of the structure represented by formula (AY1) and the structure represented by formula (DY1). Furthermore, the molar amount of the amide ester structure in resin A is 90 to 99.9% relative to the total molar amount of the amide acid structure and the amide ester structure. In addition, the amine value of resin A is 0.0010 to 0.3000 mmol / g.

[0101] The resin A (specific resin) in the resin composition of the present invention may be composed of one type of resin or two or more types of resin. When resin A (specific resin) is composed of two or more types of resin, the esterification rate, amine value, imidization rate, acid value, and unit structure ratio are values ​​calculated or measured by treating the above-mentioned multiple resins as one type of resin.

[0102] The specific resin is preferably a polyimide precursor and may contain polyimide.

[0103] Polyimide precursors refer to resins that become polyimides through changes in their chemical structure caused by external stimuli, preferably resins that become polyimides through changes in their chemical structure caused by heat, and more preferably resins that become polyimides through a ring-closing reaction caused by heat to form a ring structure.

[0104] 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.

[0105] 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.

[0106] In this specification, "main chain" refers to the longest bonded chain in the resin molecule, and "side chain" refers to all other bonded chains.

[0107] 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.

[0108] 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 ring members. The imide ring structure is preferably a 5-membered ring.

[0109] In addition to the imide group, polyimide can also be a so-called polyamide-imide having an amide group within the 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.

[0110] As will be described later, both amide ester structures and amide acid structures contain an amide group.

[0111] [Esterification rate]

[0112] The molar ratio (esterification rate) of the amamide ester structure in a specific resin relative to the total molar ratio of the amamide acid structure and the amamide ester structure is 90.00 to 99.90%.

[0113] Amide acid structures, for example, are as follows: In the repeating unit represented by formula (1-b) described later, A 2 For -O- and R 2bWhen it is a hydrogen atom, there exists one A in the repeating unit represented by equation (1-c). 3 For -O- and R 3c When it is a hydrogen atom, there exists one, and A in the repeating unit represented by equation (1-d). 41 and A 42 Both are -O- and R 41 and R 42 There are two when both are hydrogen atoms. For example, the amide ester structure is as follows: In the repeating unit represented by formula (1-b), A... 2 For -O- and R 2b When it is a monovalent organic group, there is one, and A exists in the repeating unit represented by formula (1-c). 3 For -O- and R 3c When it is a monovalent organic group, there is one, and A exists in the repeating unit represented by formula (1-d). 41 and A 42 Both are -O- and R 41 and R 42 There are two when both are monovalent organic groups.

[0114] It is believed that the side-chain carboxylic acid groups in the resin, within the aforementioned predetermined esterification rate and with an amine value within a specific range, can buffer against environmental amines. The esterification rate is more preferably 92.00–99.50%, and even more preferably 95.00–99.00%.

[0115] Furthermore, when a particular resin is composed of multiple resins, the esterification rate calculated by treating the multiple resins as a single resin is within the aforementioned range.

[0116] The esterification rate is set to the resin. 1 The value is obtained by H-NMR measurement. Specifically, it can be obtained by the measurement method described in the examples below.

[0117] [Imidification rate]

[0118] The imidization rate of a specific resin is preferably 3 to 40%.

[0119] From the viewpoint of elongation at break, the imidization rate is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.

[0120] Furthermore, from the viewpoint of resolution, the imidization rate is preferably less than 40%, more preferably less than 35%, further preferably less than 30%, and especially preferably less than 25%.

[0121] In this invention, the imidization rate refers to the value calculated by the following method.

[0122] The resin is dissolved in γ-butyrolactone and diluted to a viscosity of 2,000 mPa·s. This solution is then applied to a silicon wafer via spin coating to form a resin layer. Since the resin has low solubility for γ-butyrolactone, if a resin layer cannot be formed, the solvent can be changed to another solvent. Solvents contained in the resin composition can also be used as other solvents; for example, NMP can be used. Furthermore, the viscosity can be appropriately varied within an adjustable range. The silicon wafer to which the obtained resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm after film formation on the silicon wafer. Here, if only a resin solution with low viscosity is obtained, and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness can be appropriately varied. For example, if the film thickness is 5 μm or more, a similar value can be obtained as the imidization rate.

[0123] The resin layer was measured using the ATR method with a Nicoletti S20 (manufactured by Thermofisher), within the measurement range of 4000–700 cm⁻¹. -1 The measurement was conducted under the condition of 50 measurements. A 1380cm... -1 Nearby (1350-1450cm) -1 (In the case of multiple peaks, the peak with the highest intensity) is the peak height divided by 1500cm. -1 Nearby (1460-1550cm) -1 The imidization index A of the resin is determined by the peak height of the peak with the highest peak intensity when multiple peaks exist. For a film heated at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min, the imidization index B is calculated using the same method. The imidization index A is divided by the imidization index B to obtain the imidization rate of the resin.

[0124] In the determination of imidization rate, for example, a resin for which the imidization rate is determined can be obtained from the composition by the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water to crystallize the resin, which is then filtered. The filtrate is recovered and dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water to crystallize the resin, filtered, and dried at 45°C for 20 hours to obtain the resin.

[0125] When determining the physical properties of specific resins, such as acid value and amine value, the resin can be obtained and the determination can be performed using the same method.

[0126] The imidization rate can be adjusted to 3-40% by appropriately changing the reaction conditions, such as the reaction temperature, during the manufacturing of a specific resin.

[0127] [Amine value]

[0128] The amine value of the specific resin is 0.0010 to 0.3000 mmol / g. It is believed that by having an amine value within a specific range and the presence of carboxylic acid groups in the side chains of the resin within a range that corresponds to the aforementioned predetermined esterification rate, it acts as a buffer against environmental amines. From the viewpoint of the storage stability of the composition, the amine value of the specific resin is more preferably 0.0100 to 0.2000 mmol / g, and even more preferably 0.0300 to 0.1000 mmol / g.

[0129] The lower limit of the above amine value is not particularly limited and can be 0.00 mmol / g.

[0130] Regarding the aforementioned amine value, a test solution was prepared by dissolving 0.62 g of resin in 50 mL of diethylene glycol dimethyl ether and then adding 10 mL of acetic acid. The neutralization point of this solution was determined by titration with a 0.01 N (0.01 mol / L) perchloric acid solution in acetic acid.

[0131] [Acid value]

[0132] The acid value of the acid groups in the specific resin with a neutralization point pH in the range of 7.0 to 12.0 is more preferably in the range of 0.0010 to 0.3000 mmol / g, more preferably in the range of 0.0100 to 0.2000 mmol / g, and even more preferably in the range of 0.0300 to 0.1000 mmol / g.

[0133] As long as the acid value of the specific resin contained in the resin composition of the present invention is in the range of 0.0010 to 0.3000 mmol / g, the acid value of each resin constituting the specific resin contained in the composition may be outside the range of 0.0010 to 0.3000 mmol / g. Specifically, two or more polymer precursors outside the range of 0.0010 to 0.3000 mmol / g may be mixed to adjust the acid value of the specific resin contained in the composition to be in the range of 0.0010 to 0.3000 mmol / g.

[0134] In the resin composition of the present invention, the resin contained in the composition preferably has an acid value of 70% or more by mass, more preferably 80% or more by mass, and even more preferably 90% or more by mass, in the range of 0.0010 to 0.3000 mmol / g.

[0135] The acid groups contained in a particular resin with a neutralization point pH range of 7.0 to 12.0 represent acid groups with a pH range of 7.0 to 12.0 in the acid value determination method described in the examples described later, and may be exemplified by carboxyl groups.

[0136] The specific resin contained in the composition of the present invention may contain acid groups other than acid groups with a pH range of 7.0 to 12.0, or may not contain them.

[0137] The acid groups contained in the specific resin included in the composition of the present invention preferably have a pH range of 7.0 to 12.0 or more of 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more of acid groups.

[0138] The acid groups with a pH range of 7.0 to 12.0 can be bonded to the side chains of a specific resin or to the main chain. Preferably, they are bonded to at least the side chains of the specific resin.

[0139] In addition, sodium hydroxide is used as a base to determine the neutralization point. Furthermore, in cases where it is difficult to determine the neutralization point using sodium hydroxide, the value obtained by determining the neutralization point using calcium hydroxide and converting it to sodium hydroxide is also considered as the value obtained by determining the neutralization point using sodium hydroxide.

[0140] The acid values ​​within the above range can be achieved by appropriately adjusting the reaction conditions.

[0141] In this invention, the specific resin is preferably manufactured using a synthetic reaction solution with a water content of 50 to 700 ppm by mass. This configuration makes it easier to obtain a specific resin that meets a predetermined acid value.

[0142] [polymeric groups]

[0143] The resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0144] In the resin composition, preferably at least the resin has polymeric groups, more preferably the resin has polymeric groups and contains polymeric compounds separately from the resin.

[0145] The polymerizable groups in a particular resin are preferably free radical polymerizable groups.

[0146] When a particular resin has free radical polymerizable groups, the resin composition of the present invention preferably contains a free radical polymerization initiator, more preferably a free radical polymerization initiator and a free radical crosslinking agent. Furthermore, a sensitizer may be included as needed. Such a resin composition can, for example, form a negative photosensitive film.

[0147] Furthermore, certain resins may have polar conversion groups such as acid-decomposing groups.

[0148] When a particular resin has acid-decomposing groups, the resin composition preferably contains a photoacid generator. Such a resin composition can be used to form, for example, chemically amplified positive or negative photosensitive films.

[0149] [Examples of resin structures]

[0150] The particular resin preferably has at least one repeating unit selected from the group consisting of repeating units represented by formula (1-b), repeating units represented by formula (1-c), and repeating units represented by formula (1-d), and may further have repeating units represented by formula (1-a).

[0151] In these, a particular resin preferably has at least one repeating unit represented by formula (1-d), more preferably has a repeating unit represented by formula (1-d) and at least one repeating unit selected from the group consisting of repeating units represented by formula (1-a), repeating units represented by formula (1-b) and repeating units represented by formula (1-c).

[0152] [Chemical Formula 7]

[0153]

[0154] In equation (1-a), X a Y is a tetravalent organic group. a It is a divalent organic group.

[0155] In equation (1-b), A 2 -O- or -NR Z -, R Z R is a hydrogen atom or a monovalent organic group. 2b X is a hydrogen atom or a monovalent organic group. b Y is a tetravalent organic group. b It is a divalent organic group.

[0156] In equation (1-c), A 3 -O- or -NR Z -, R Z R is a hydrogen atom or a monovalent organic group. 3c X is a hydrogen atom or a monovalent organic group. c Y is a tetravalent organic group. c It is a divalent organic group.

[0157] In equation (1-d), A 41 and A 42 Each can be independently -O- or -NR. Z -, R Z R is a hydrogen atom or a monovalent organic group. 41 and R 42 Each is independently a hydrogen atom or a monovalent organic group, X d Y is a tetravalent organic group. d It is a divalent organic group.

[0158] [X] a]

[0159] In equation (1-a), X a The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40.

[0160] In equation (1-a), X a Preferably, it is any of the structures represented by formulas (2a) to (2e) below, or a structure containing the structure after removing two or more hydrogen atoms from the structure represented by formula (V-4) below.

[0161] [Chemical Formula 8]

[0162]

[0163] In equations (2a) to (2e), L 1 and L 2 Each of the above represents a divalent group or single bond that is not conjugated with the benzene ring to which it is bonded. *1 to *4 represent the bonding sites with the carbonyl groups described in formula (1-a), (1-b), (1-c), or (1-d), respectively. The hydrogen atoms in these structures can be substituted by substituents.

[0164] In equation (V-4), n1 represents an integer greater than or equal to 1.

[0165] In equation (2c), L 1 and L 2 Each is preferably -CH2- or -O-, independently.

[0166] In formulas (2a) to (2e), the hydrogen atoms can be replaced by substituents. Examples of substituents include alkyl groups and halogenated alkyl groups, preferably alkyl groups with 1 to 4 carbon atoms or halogenated alkyl groups with 1 to 4 carbon atoms, and more preferably methyl or trifluoromethyl. A halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. As a halogen atom, preferably F or Cl, and more preferably F.

[0167] In formula (V-4), n1 is preferably an integer from 1 to 5, more preferably 1 or 2, and even more preferably 1.

[0168] In X a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), X a Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents X in formula (1-a). a The bonding sites of the four carbonyl groups. Furthermore, the definition and preferred embodiment of n1 are as described above. Additionally, the hydrogen atoms in the following structure can be further substituted with known substituents such as hydrocarbon groups.

[0169] [Chemical Formula 9]

[0170]

[0171] Furthermore, in equation (1-a), X a It is also preferred to include a structure after removing two or more hydrogen atoms from the structure represented by any one of the following formulas (V-1), (V-2), (V-3) and (V-5).

[0172] [Chemical Formula 10]

[0173]

[0174] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0175] 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.

[0176] In equation (V-2), R X1 Each of the components is preferably an alkyl group or a haloalkyl group, more preferably an alkyl group 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.

[0177] In equation (V-3), R X2 and R X3 Each atom is preferably a hydrogen atom.

[0178] 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, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

[0179] In X a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), X a Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (1-a). aThe bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0180] [Chemical Formula 11]

[0181]

[0182] In X a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), X a Preferably, the group is represented by the following formula (V-2-1). In this specification, a bond crossing the edge of the ring structure indicates substitution for any one of the hydrogen atoms in the ring structure. In the following formula, * indicates substitution for X in formula (1-a). a The bonding sites of the four carbonyl groups. Furthermore, R X1 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0183] [Chemical Formula 12]

[0184]

[0185] In X a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), X a 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 formula, * represents X in formula (1-a). a The bonding sites of the four carbonyl groups. Furthermore, R X2 and R X3 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0186] [Chemical Formula 13]

[0187]

[0188] In X a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), X a Preferably, it is a group represented by the following formula (V-5-1). In the following formula, * represents X in formula (1-a). a The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0189] [Chemical Formula 14]

[0190]

[0191] In addition, X a It can be the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride as described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0192] And, X a Preferably, the structure does not contain imide bonds.

[0193] And, X a Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0194] 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.

[0195] 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.

[0196] In addition, X a Preferably, the structure does not contain ester bonds.

[0197] In this invention, the ester bond is represented by *-OC (=O)-*.

[0198] Among these, X a 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.

[0199] [Y] a ]

[0200] In equation (1-a), Y a The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40.

[0201] In equation (1-a), Y aIt can be a group that includes a structure after removing two or more hydrogen atoms from the structure represented by any of the following formulas (V-1) to (V-10).

[0202] The chemical resistance and flatness of the cured material are improved by adding groups to the structure containing the structure represented by any one of formulas (V-1) to (V-10) after removing two or more hydrogen atoms.

[0203] [Chemical Formula 15]

[0204]

[0205] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0206] 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.

[0207] In equation (V-8), R X5 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0208] In equation (V-2), R X1 Each of the components is preferably an alkyl group or a haloalkyl group, more preferably an alkyl group 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.

[0209] In equation (V-3), R X2 and R X3 Each atom is preferably a hydrogen atom, independently and separately. 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, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

[0210] In equation (V-8), R X5Each of the components is preferably an alkyl group or a haloalkyl group, more preferably an alkyl group 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.

[0211] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y a 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-a). a The bonding sites of the two nitrogen atoms are denoted by n1, which is an integer from 0 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0212] [Chemical Formula 16]

[0213]

[0214] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y a 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-a). a The bonding sites of the two nitrogen atoms. Furthermore, R X1 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0215] [Chemical Formula 17]

[0216]

[0217] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y a 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 formula, * represents Y in formula (1-a). a The bonding sites of the two nitrogen atoms. Furthermore, R X2 and R X3The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0218] [Chemical Formula 18]

[0219]

[0220] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y a Preferably, it is a group represented by the following formula (V-4-2) or formula (V-4-3). In the following formulas, * represents the group corresponding to Y in formula (1-a). a In the bonding site of the two nitrogen atoms, n1 represents an integer from 0 to 5. Furthermore, n1 being 0 is also one of the preferred embodiments of the present invention. Moreover, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, alkyl halides, and halogen atoms.

[0221] [Chemical Formula 19]

[0222]

[0223] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), Y a 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-a). a The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in formula (V-5-2) can be further replaced by known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms. Preferably, the hydrogen atoms in the groups represented by formula (V-5-2) are not substituted.

[0224] [Chemical Formula 20]

[0225]

[0226] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), Y a 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-a). a The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0227] [Chemical Formula 21]

[0228]

[0229] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), Y a 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-a). a The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0230] [Chemical Formula 22]

[0231]

[0232] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), Y a 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-a). a The bonding sites of the two nitrogen atoms. Furthermore, R X5 The definition and preferred method are as described above. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0233] [Chemical Formula 23]

[0234]

[0235] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), Y a 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-a). a The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0236] [Chemical Formula 24]

[0237]

[0238] In Y a In the case of a group comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10), Y a 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-a).a The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0239] [Chemical Formula 25]

[0240]

[0241] In addition, Y a It can be the group described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421.

[0242] Furthermore, Y a Preferably, the structure does not contain an imide structure.

[0243] Furthermore, Y a Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0244] In addition, Y a Preferably, the structure does not contain ester bonds.

[0245] Among these, Y a 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.

[0246] [X] b Y b ]

[0247] X in equation (1-b) b and Y b The preferred method is the same as X in equation (1-a) a and Y a The preferred method is the same. Wherein, X a and Y a The description of “Formula (1-a)” is read as “Formula (1-b)”.

[0248] [A] 2 ]

[0249] A in equation (1-b) 2 Indicates -O- or -NR z -, preferably -O-.

[0250] R z It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0251] [R] 2b ]

[0252] R in equation (1-b) 2bThis represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group comprises a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxide group.

[0253] Furthermore, R 2b Preferably, it contains polymerizable groups. These polymerizable groups are groups capable of cross-linking reactions through heat, free radicals, etc., and are preferably free radical polymerizable groups. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. As a free radical polymerizable group present in a particular resin, a group having olefinic unsaturated bonds is preferred.

[0254] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, and groups represented by formula (III) below, with groups represented by formula (III) below being preferred.

[0255] [Chemical Formula 26]

[0256]

[0257] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0258] In equation (III), * indicates the bonding site with other structures.

[0259] In equation (III), R 201 It represents alkylene groups with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, cycloalkylene groups, or polyalkylene groups.

[0260] Regarding the preferred R 201 Examples include alkylene compounds such as ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, and polyalkylene oxides, more preferably alkylene compounds such as ethylene and propyleneene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxides, and even more preferably alkylene compounds such as ethylene and propyleneene or polyalkylene oxides.

[0261] In this invention, polyalkylene oxide refers to a group formed by the direct bonding of two or more alkene oxides. The alkylene oxides in the multiple alkene oxides contained in the polyalkylene oxide can be the same or different.

[0262] When a polyalkylene oxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkylene oxide can be random, block-shaped, or alternating.

[0263] The number of carbon atoms in the alkylene group (the number of carbon atoms including the substituent if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

[0264] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0265] Furthermore, the number of alkene oxides contained in the polyalkylene oxide (the number of repetitions of the polyalkylene oxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0266] From the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or groups formed by the bonding of multiple ethyleneoxy and multiple propyleneoxy groups are preferred as polyethyleneoxy or polypropyleneoxy groups, and polyethyleneoxy is even more preferred. Among the aforementioned groups formed by the bonding of multiple ethyleneoxy and multiple propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, form blocks, or be arranged in an alternating pattern. The preferred manner for the number of repetitions of the ethyleneoxy groups, etc., in these groups is as described above.

[0267] In equation (1-b), in R 2b In the case of hydrogen atoms, certain resins can form countersalts with tertiary amine compounds having olefinic unsaturated bonds. N,N-dimethylaminopropyl methacrylate is an example of such a tertiary amine compound having olefinic unsaturated bonds.

[0268] In equation (1-b), R 2b It can be a polarity-converting group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes through the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups. Preferably, it is an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. From the point of view of exposure sensitivity, it is more preferred to be an acetal group or a ketal group.

[0269] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0270] [X] c Y c A 3 R 3c ]

[0271] X in equation (1-c) c and Y c The preferred method is the same as X in equation (1-a) a and Y a The preferred method is the same. Wherein, X a and Y a The description of “Formula (1-a)” is read as “Formula (1-c)”.

[0272] A in equation (1-c) 3 and R 3c The preferred method is the same as A in equation (1-b). 2 and R 2b The preferred method is the same. Among them, A 2 and R 2b The description of “Formula (1-b)” is read as “Formula (1-c)”.

[0273] [X] d Y d A 41 A 42 R 41 R 42 ]

[0274] X in equation (1-d) d and Y d The preferred method is the same as X in equation (1-a) a and Y a The preferred method is the same. Wherein, X a and Y a The description of “Formula (1-a)” is read as “Formula (1-d)”.

[0275] A in equation (1-d) 41 and A 42 The preferred methods are respectively related to A in equation (1-b) 2 The preferred method is the same. Among them, A 2 The description of “Formula (1-b)” is read as “Formula (1-d)”.

[0276] R in equation (1-d) 41 and R 42 The preferred methods are respectively related to R in equation (1-b) 2b The preferred method is the same. Among them, R 2b The description of “Formula (1-b)” is read as “Formula (1-d)”.

[0277] Here, among all the repeating units represented by formula (1-b), formula (1-c), and formula (1-d) contained in a particular resin, relative to R 2b and R 3c R 41 and R 42 The total molar amount, R 2b and R 3c R 41 and R 42 The proportion of those groups that are monovalent organic groups is preferably 50.0-100%, more preferably 85.0-100%, and even more preferably 92.0-100%.

[0278] The specific resin preferably contains at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2, repeating unit A-3 and repeating unit A-4.

[0279] Repeating unit A-1: ​​represented by the above formula (1-a) and X a A repeating unit of any of the structures represented by equations (2a) to (2e), or a repeating unit comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0280] Repeating unit A-2: represented by the above equation (1-b) and X b A repeating unit of any of the structures represented by equations (2a) to (2e), or a repeating unit comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0281] Repeating unit A-3: represented by the above formula (1-c) and X c A repeating unit of any of the structures represented by equations (2a) to (2e), or a repeating unit comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0282] Repeating unit A-4: represented by the above formula (1-d) and X d A repeating unit of any of the structures represented by equations (2a) to (2e), or a repeating unit comprising a structure obtained by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0283] In these, a particular resin preferably contains repeating unit A-4, more preferably has repeating unit A-4 and at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2 and repeating unit A-3.

[0284] The specific resin preferably contains at least one repeating unit selected from the group consisting of repeating unit B-1, repeating unit B-2, repeating unit B-3 and repeating unit B-4.

[0285] In particular, the specific resin preferably includes at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2, repeating unit A-3 and repeating unit A-4, and at least one repeating unit selected from the group consisting of repeating unit B-1, repeating unit B-2, repeating unit B-3 and repeating unit B-4.

[0286] The specific resin preferably includes repeating unit A-4 and repeating unit B-4.

[0287] Repeating unit B-1: represented by the above formula (1-a) and X a Repeating units comprising structures obtained by removing two or more hydrogen atoms from the structures represented by any one of equations (V-1), (V-2), (V-3), and (V-5).

[0288] Repeating unit B-2: represented by the above equation (1-b) and X b Repeating units comprising structures obtained by removing two or more hydrogen atoms from the structures represented by any one of equations (V-1), (V-2), (V-3), and (V-5).

[0289] Repeating unit B-3: represented by the above formula (1-c) and X c Repeating units comprising structures obtained by removing two or more hydrogen atoms from the structures represented by any one of equations (V-1), (V-2), (V-3), and (V-5).

[0290] Repeating unit B-4: represented by the above formula (1-d) and X d Repeating units comprising structures obtained by removing two or more hydrogen atoms from the structures represented by any one of equations (V-1), (V-2), (V-3), and (V-5).

[0291] The specific resin preferably comprises the resin selected from the above formula (1-b) and R 2b A repeating unit having a monovalent organic group with an olefinic unsaturated bond, represented by the above formula (1-c) and R 3c A repeating unit having a monovalent organic group with an olefinic unsaturated bond, and R represented by the above formula (1-d) 41 and R42 At least one of the repeating units is a repeating unit from the group consisting of repeating units having a monovalent organic group with an olefinic unsaturated bond, more preferably including the repeating unit represented by formula (1-d) above and R 41 and R 42 At least one of them is a repeating unit with a monovalent organic group having an olefinic unsaturated bond.

[0292] A particular resin preferably comprises the resin selected from the one represented by formula (1-a) above, and Y a The repeating unit of the structure represented by equations (C-1) to (C-3), and the structure represented by equation (1-b) above, and Y b A repeating unit of a structure comprising the structures represented by equations (C-1) to (C-3) below, and the structure represented by equation (1-c) above, and Y c The repeating unit of the structure represented by equations (C-1) to (C-3) and the structure represented by equation (1-d) above, and Y d It is at least one repeating unit in a group consisting of repeating units of structures that include the structures represented by equations (C-1) to (C-3).

[0293] Here, equation (1-a) represents Y a The repeating unit of the structure that includes the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit belonging to repeating unit A-1 or repeating unit B-1.

[0294] Here, equation (1-b) represents Y b The repeating unit of the structure that includes the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit belonging to repeating unit A-2 or repeating unit B-2.

[0295] Here, equation (1-c) represents Y c The repeating unit of the structure that includes the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit belonging to repeating unit A-3 or repeating unit B-3.

[0296] Here, equation (1-d) represents Y d The repeating unit of the structure that includes the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit belonging to repeating unit A-4 or repeating unit B-4.

[0297] As one embodiment of the specific resin in this invention, examples can be given where the total content of the repeating units represented by formulas (1-a), (1-b), (1-c), or (1-d) is 50 mol% or more of the total repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the specific resin, except for the end units, can be repeating units represented by formulas (1-a), (1-b), (1-c), or (1-d).

[0298] Furthermore, as another embodiment of the specific resin in this invention, an example is provided where the total content of the repeating units represented by formula (1-d) is 50 mol% or more of the total repeating units. More preferably, the total content is 60 mol% or more, further preferably 70 mol% or more, and especially preferably 80 mol% or more. The upper limit of the total content is preferably 97 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, and especially preferably 85 mol% or less.

[0299] Furthermore, the total content of repeating units (also referred to as "repeating unit A") belonging to repeating unit A-1, repeating unit A-2, repeating unit A-3, or repeating unit A-4 in the specific resin of the present invention is preferably 20 mol% or more of all repeating units. More preferably, the total content is 30 mol% or more, further preferably 40 mol% or more, and particularly preferably 50 mol% or more. The upper limit of the total content is not particularly limited; all repeating units in the specific resin except for the terminal units can be repeating unit A.

[0300] Furthermore, the total content of the specific resin in this invention belonging to repeating unit B-1, repeating unit B-2, repeating unit B-3 or repeating unit B-4 (also referred to as "repeating unit B") is preferably 0 to 80 mol% of all repeating units. The above total content is more preferably 5 to 70 mol%, further preferably 10 to 60 mol%, and especially preferably 15 to 50 mol%.

[0301] Furthermore, the total content of repeating unit A and repeating unit B in the specific resin of the present invention is preferably 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the specific resin except for the terminal units can be repeating unit A or repeating unit B.

[0302] In one aspect of the invention, from the viewpoint of resin orientation and raw material availability, a particular resin is particularly preferred to include the structure represented by the formula (1-dp-2d1).

[0303] [Chemical Formula 27]

[0304]

[0305] In the formula, * indicates the bonding site with other structures.

[0306] The structure represented by equation (1-dp-2d1) is a partial structure of the repeating unit represented by equation (1-d), which is equivalent to X. d For the structure represented by equation (2d), A 41 and A 42 All are -O-, R 41 and R 42 All of them have the structure of methacryloyloxyethyl. When a particular resin includes the structure represented by formula (1-dp-2d1), the repeating unit of the structure represented by formula (1-dp-2d1) preferably includes 10 mol% or more of the total repeating unit, more preferably 20 mol% or more, even more preferably 30 mol% or more, preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0307] When a particular resin contains the structure represented by formula (1-dp-2d1), the particular resin preferably further contains at least one of the structures represented by formula (1-dp-V1-1) and formula (Y-V1-1).

[0308] [Chemical Formula 28]

[0309]

[0310] In the formula, * indicates the bonding site with other structures.

[0311] The structure represented by equation (1-dp-V1-1) is a partial structure of the repeating unit represented by equation (1-d), which is equivalent to X. d The structure after removing 4 hydrogen atoms from the structure represented by formula (V-1), A 41 and A 42 All are -O-, R 41 and R 42 Both have the structure of methacryloyloxyethyl.

[0312] The structure represented by equation (Y-V1-1) is equivalent to Y in the repeating unit represented by, for example, equation (1-b). bThe structure obtained by removing two hydrogen atoms from the structure represented by equation (V-1), and the Y in the repeating unit represented by equation (1-d) d This is a possible structure when two hydrogen atoms are removed from the structure represented by formula (V-1). The structure represented by formula (Y-V1-1) can be combined with the structure represented by formula (1-dp-2d1) to form the repeating unit represented by formula (1-d).

[0313] When a particular resin contains the structure represented by formula (1-dp-V1-1) or the structure represented by formula (Y-V1-1), the repeating unit containing either of these structures preferably contains 10 mol% or more of the total repeating unit, more preferably 20 mol% or more, even more preferably 30 mol% or more, preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0314] [The structure represented by equation (AY1) and the structure represented by equation (DY1)]

[0315] The specific resin comprises at least one structure selected from the group consisting of the structure represented by formula (AY1) and the structure represented by formula (DY1). This structure is a small and robust resin framework structure, thus allowing molecules to pack tightly. Therefore, when the resin composition of the present invention is used in semiconductor manufacturing, etc., the penetration of environmental amines or developer components into the film is suppressed, reducing the influence of position-dependent effects within the wafer plane.

[0316] [Chemical Formula 29]

[0317]

[0318] In formula (AY1), * indicates the bonding site with other structures, and X is the group represented by formula (2a). In formula (2a), *1 to *4 represent the bonding sites with carbonyl groups, and the bonding positions are not limited.

[0319] [Chemical Formula 30]

[0320]

[0321] In formula (DY1), Y is any group selected from the following. * indicates the bonding site with nitrogen.

[0322] [Chemical Formula 31]

[0323]

[0324] The structure represented by equation (AY1) is a partial structure of the repeating unit represented by equation (1-d), which is equivalent to X. dThe group represented by formula (2a), A 41 and A 42 All are -O-, R 41 and R 42 Both have the structure of methacryloyloxyethyl.

[0325] In a particular resin, the repeating units of the structure selected from the group consisting of the structure represented by formula (AY1) and the structure represented by formula (DY1) preferably comprise 20 mol% or more of the total repeating units, more preferably 30 mol% or more, even more preferably 50 mol% or more, preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0326] [Specific structures in resin]

[0327] The specific resin preferably contains the structure represented by formula (1) (specific structure).

[0328] The preferred configuration of the structure represented by equation (1) will be described later.

[0329] In the case where a particular resin contains the structure represented by formula (1), the particular resin may have the structure represented by formula (1) on the main chain, but preferably on the side chain.

[0330] In this specification, "main chain" refers to the longest bonded chain in the polymer compound that constitutes the resin, and "side chain" refers to the other bonded chains.

[0331] As an example of a specific resin structure comprising the structure represented by formula (1), a structure satisfying at least one of the following can be given. (* indicates that it is related to X) b X c or X d (The bond position.)

[0332] • The *-C (=O)-A in the repeating unit represented by equation (1-b) 2 -R 2b Repeating units are formed by replacing groups that contain the structure represented by formula (1).

[0333] • The *-C (=O)-A in the repeating unit represented by equation (1-c) 3 -R 3c Repeating units are formed by replacing groups that contain the structure represented by formula (1).

[0334] • The *-C (=O)-A in the repeating unit represented by equation (1-d) 41 -R 41 *-C(=O)-A42 -R 42 The repeating unit is formed by replacing any one or more of the groups in the structure represented by formula (1).

[0335] • A structure having the structure represented by formula (1) shown below is included on the imide ring at the end of a particular resin.

[0336] [Chemical Formula 32]

[0337]

[0338] In the formula, R 132 R represents a tetravalent organic group. X1 and R X2 Each of the radicals or organic groups that independently represent the structure represented by formula (1), R X1 and R X2 At least one of them is a group that includes the structure represented by formula (1).

[0339] As a preferred example of "a group that includes the structure represented by formula (1)," the group represented by formula (X-1) described later can be cited.

[0340] The resin composition may contain a specific resin having the structure represented by formula (1) and a specific resin not having the structure represented by formula (1).

[0341] The content of the structure represented by formula (1) in a particular resin is preferably 0.01 to 1.0 mmol / g, more preferably 0.01 to 0.85 mmol / g.

[0342] [Molecular weight]

[0343] The weight-average molecular weight (Mw) of a particular resin is preferably 120,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less.

[0344] Furthermore, the aforementioned Mw is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. The weight-average molecular weight (Mw) of a particular resin is particularly preferably 15,000 to 40,000.

[0345] The number average molecular weight (Mn) of the specific resin is preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less.

[0346] Furthermore, the Mn is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.

[0347] The molecular weight dispersion of the aforementioned 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 upper limit to the molecular weight dispersion of the specific resin; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0348] In this specification, the molecular weight dispersion is a value calculated based on weight-average molecular weight / number-average molecular weight.

[0349] When the resin composition comprises multiple resins as a specific resin, 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. Furthermore, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple resins are considered as a single resin are each within the above-mentioned ranges.

[0350] [Manufacturing method of specific resins]

[0351] The specific resin is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by reacting the dicarboxylic acid or a dicarboxylic acid derivative with a diamine after halogenating it with a halogenating agent such as thionyl chloride.

[0352] Furthermore, it is preferable to use a non-halogenated catalyst instead of the aforementioned halogenating agent for the synthesis. As the aforementioned non-halogenated catalyst, known amidation catalysts that do not contain halogen atoms can be used without particular limitation; examples include boron oxide trimers, N-hydroxy compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds. Examples of the aforementioned carbodiimide compounds include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, and (2,6-diisopropylphenyl)carbodiimide.

[0353] In the manufacturing method of a specific resin, an organic solvent is preferably used during the reaction. The organic solvent can be one type or two or more types.

[0354] As an organic solvent, it can be appropriately selected according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether, N-methylpyrrolidone and N-ethylpyrrolidone.

[0355] -End- Capping Agent-

[0356] In the manufacturing method of a specific resin, to further improve storage stability, it is preferable to use end-capping agents such as acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds to end-cap the polyimide precursor and other components. As end-capping agents, monoamines are more preferred, and preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, 1-carboxyl- 5-Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0357] -Solid precipitation-

[0358] In the manufacture of certain resins, a process for precipitating solids may also be included. Specifically, polyimide precursors and the like in the reaction solution are precipitated in water and dissolved in a solvent that the specific resin can dissolve, such as tetrahydrofuran, thereby precipitating solids.

[0359] Then, the specific resin is dried to obtain the specific resin in powder form.

[0360] -Introduction of the structure represented by equation (1)-

[0361] In the case where a particular resin contains the structure represented by formula (1), the particular resin is synthesized, for example, by the method described in (1) or (2) below.

[0362] (1) In the above-mentioned specific resin manufacturing method, the carbodiimide compound is used as a non-halogen catalyst, and the reaction time, reaction temperature and the timing of the addition of the carbodiimide compound are appropriately adjusted.

[0363] (2) The polyimide precursor obtained by the above-described method for manufacturing the specific resin is reacted with a carbodiimide compound in a solvent.

[0364] As specific examples of these methods, the methods described in the synthesis examples described later can be cited, but are not limited to these.

[0365] 〔content〕

[0366] 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, and even more preferably 50% 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.

[0367] <Other Resins>

[0368] The resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0369] Other resins that can be cited include polybenzoxazole precursors, polybenzoxazole, polyamides that are not polyimide precursors, phenolic resins, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, polyurethane resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins.

[0370] For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

[0371] For example, by adding (meth)acrylic resin to the resin composition in place of the polymerizable compound described later, or by adding (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc., can be improved. The (meth)acrylic resin has a weight-average molecular weight of 20,000 or less and a high value of polymerizable groups (e.g., the molar amount of polymerizable groups in 1g of resin is 1×10⁻⁶). -3 (more than moles / g).

[0372] 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.

[0373] 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 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.

[0374] 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.

[0375] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When containing two or more resins, it is preferable that the total amount is within the above-mentioned range.

[0376] <Photosensitive agent>

[0377] The resin composition contains a photosensitizer (photosensor B).

[0378] Examples of photosensitizers include photopolymerization initiators and photoacid generators, with photopolymerization initiators being preferred.

[0379] [Photopolymerization initiator]

[0380] The resin composition of the present invention preferably contains a photopolymerization initiator.

[0381] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on 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, it can also be an active agent that reacts with a photoexcited sensitizer to generate active free radicals.

[0382] 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 -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be determined using known methods. For example, it is preferred 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.

[0383] As photoradical polymerization initiators, any known compounds can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl biimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azido compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0384] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference, can be cited. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0385] 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 as described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators as described in Japanese Patent No. 4225898 can be used, as these contents are incorporated herein by reference.

[0386] 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.

[0387] 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.

[0388] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may also be used, for example. This content is incorporated herein by reference.

[0389] Oxime compounds are more preferably chosen as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also function as photocuring accelerators.

[0390] 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.

[0391] Preferred oxime compounds include, for example, compounds with the following structures, or 3-(benzoyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propionyloxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one, 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.

[0392] [Chemical Formula 33]

[0393]

[0394] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05 (all manufactured by BASF), ADEKA OPTOMERN-1919 (manufactured by ADEKA CORPORATION, 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 Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Oxime compounds with the following structures can also be used.

[0395] [Chemical Formula 34]

[0396]

[0397] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring, oxime compounds having at least one benzene ring forming a naphthalene ring skeleton, and oxime compounds having fluorine atoms can also be used.

[0398] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, are also permitted to be used. These contents are incorporated herein by reference.

[0399] 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 this specification.

[0400] 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.

[0401] In addition, photopolymerization initiators sometimes 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.

[0402] [Two or more polymerization initiators, etc.]

[0403] The resin composition of the present invention may contain two or more polymerization initiators as polymerization initiators.

[0404] 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.

[0405] 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.

[0406] By incorporating photoradical polymerization initiators and photoacid generators, performance characteristics such as resolution can sometimes be improved.

[0407] As for the content ratio of the photoradical polymerization initiator and the photoacid generator, the content of the photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photoradical polymerization initiator and the photoacid generator.

[0408] [Thermal polymerization initiator]

[0409] 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.

[0410] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated herein by reference, can be cited as thermal free radical polymerization initiators.

[0411] 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 resin composition may contain only one thermal polymerization initiator or may contain two or more. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0412] <Aniline Compounds>

[0413] From a resolution point of view, the resin composition preferably contains an aniline compound.

[0414] The aniline compound is preferably a compound that functions as a sensitizer, and more preferably a compound that sensitizes photoradical polymerization initiators.

[0415] Sensitizers absorb specific active radiation and become electronically excited. When these sensitizers come into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., electron transfer, energy transfer, and heating occur. Consequently, the thermal free radical polymerization initiators and photofree radical polymerization initiators undergo chemical changes and decompose, generating free radicals, acids, or bases.

[0416] Furthermore, if a portion of the aniline compound remains in the cured material, it can sometimes quench acids generated in the cured material or acids introduced from outside the cured material, and inhibit the oxidation of the metal, resulting in improved adhesion.

[0417] As aniline compounds, preferably are compounds containing a benzene ring structure having dialkylamino or dihydroxyalkylamino as substituents.

[0418] Examples of aniline compounds include, for example, milchone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylindanone, and p-dimethylaminophenylmethyleneindanone. 2-(p-Dimethylaminophenylene)-benzothiazole, 2-(p-Dimethylaminophenylene)benzothiazole, 2-(p-Dimethylaminophenylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminophenylene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyl Oxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, dimethylaniline, bis(4-dimethylaminophenyl) Methane, 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, and aniline compounds in the examples described below.

[0419] Among these, the preferred aniline compound is one represented by the following formula (AN-1) or the following formula (AN-2) (hereinafter also referred to as "compound A").

[0420] [Chemical Formula 35]

[0421]

[0422] In equation (AN-1), R 11 and R 12 Each can independently represent a hydrogen atom or a monovalent organic group, R 11 and R 12 At least one of them contains the group represented by formula (R-1), Ar 1X represents an aromatic ring structure that can have substituents or condensed rings. n1 represents an integer greater than 2. When n1 is 2, X represents a single bond or a divalent linker. When n1 is 3 or greater, X represents an n1-valent linker.

[0423] In equation (AN-2), R 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, R 21 and R 22 At least one of them contains the group represented by formula (R-1), Ar 2 This indicates an aromatic ring structure that can have substituents or condensed rings, and n2 represents an integer greater than or equal to 1.

[0424] [Chemical Formula 36]

[0425]

[0426] In equation (R-1), R R1 and R R2 Each of the m R atoms independently represents a hydrogen atom or a monovalent organic group. R1 They can be the same or different, m R R2 They can be the same or different, m represents an integer greater than 2, and * represents the bonding site with other structures.

[0427] In formula (AN-1), R is preferred. 11 and R 12 All of them are groups represented by formula (R-1).

[0428] In R 11 and R 12 When one of them is a hydrogen atom or a monovalent organic group different from the group represented by formula (R-1), R is preferred. 11 and R 12 The other one is a monovalent organic group that is different from the group represented by formula (R-1).

[0429] Examples of monovalent organic groups that are different from the group represented by formula (R-1) include alkyl, aryl, etc., preferably alkyl, and more preferably methyl.

[0430] In the group represented by formula (R-1), R R1 and R R2 Each of these can independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group. Furthermore, R R1 and R R2 Using only hydrogen atoms is also a preferred method.

[0431] In formula (R-1), m represents an integer of 2 or more, preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0432] The following are specific examples of the groups represented by formula (R-1), but the present invention is not limited thereto. In the following specific examples, the meaning of * is the same as that of * in formula (R-1).

[0433] [Chemical Formula 37]

[0434]

[0435] In equation (AN-1), Ar 1 This indicates an aromatic ring structure that can have substituents or condensed rings.

[0436] In equation (AN-1), Ar is... 1 The aromatic ring structure in the structure can be any of the aromatic hydrocarbon ring structure or the aromatic heterocyclic structure, but is preferably an aromatic hydrocarbon ring structure, and more preferably a benzene ring structure.

[0437] Examples of substituents include alkyl, aryl, and halogen atoms, with alkyl being preferred and methyl being more preferred.

[0438] Examples of cycloalkanes and aromatic rings can be used as cyclocondensed rings, with cyclopropane rings being the most preferred.

[0439] In formula (AN-1), n1 represents an integer from 2 to 4, preferably 2 or 3, and more preferably 2.

[0440] In formula (AN-1), when n1 is 2, X represents a single bond or a divalent linker. Preferably, the divalent linker is an alkylene group, a haloalkylene group, an aryl group, or a combination thereof. The hydrogen atom in these groups can be replaced by known substituents such as hydroxyl groups or halogen atoms.

[0441] The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene, ethylene, or isopropylene group.

[0442] The aforementioned arylene group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group, and more preferably a phenylene group.

[0443] In formula (AN-1), when n1 is 3 or more, X represents an n1-valent linking group. Preferably, the aforementioned n1-valent linking group is an aliphatic hydrocarbon group, an aromatic group, or a combination thereof. The hydrogen atoms in these groups can be replaced by known substituents such as hydroxyl groups.

[0444] The aliphatic hydrocarbon group mentioned above is preferably a saturated aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group with 1 to 4 carbon atoms.

[0445] The aromatic group described above is preferably an aromatic hydrocarbon group, and more preferably an aromatic hydrocarbon group with 6 carbon atoms.

[0446] In equation (AN-2), R 21 and R 22 The preferred method is the same as R in equation (AN-1) 11 and R 12 The preferred method is the same.

[0447] In equation (AN-2), Ar 2 This indicates an aromatic ring structure that can have substituents or condensed rings.

[0448] Examples of aromatic ring structures include benzene ring structures, carbazole ring structures, and fluorene ring structures.

[0449] Examples of substituents include alkyl, aryl, and halogen atoms, with alkyl being preferred and methyl being more preferred.

[0450] Examples of cycloalkanes and aromatic rings can be used as cyclocondensed rings, with cyclopropane rings being the most preferred.

[0451] The following are examples of Ar 2 These are specific examples, but the invention is not limited thereto. In the following specific examples, * indicates a bonding site with a nitrogen atom in formula (AN-2).

[0452] [Chemical Formula 38]

[0453]

[0454] In formula (AN-2), n2 is preferably an integer from 1 to 3, and more preferably 1 or 2.

[0455] Among these, it is preferable that compound A is a compound represented by the above formula (AN-1), wherein R in the above formula (AN-1) is... 11 and R 12 All are groups represented by formula (R-1) and m in formula (R-1) is 2.

[0456] Preferred methods for other symbols in the above method are as described in the explanation of the above formula (AN-1).

[0457] The molecular weight of compound A is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less.

[0458] The lower limit of the above molecular weight is not particularly limited, but is preferably 150 or more, and more preferably 200 or more.

[0459] When the resin composition contains an aniline compound, the content of the aniline compound relative to the total solid 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. Aniline compounds may be used alone or in combination of two or more.

[0460] Furthermore, other sensitizing pigments can be used as sensitizers.

[0461] As usable sensitizers, compounds such as benzophenone, michidone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0462] 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.

[0463] <Chain transfer agent>

[0464] 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 preferably used.

[0465] 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.

[0466] 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 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-mentioned range.

[0467] <Specific Structure>

[0468] The resin composition of the present invention preferably comprises the structure (specific structure) represented by formula (1). In formula (1), * 1 and* 2 Each can be used to independently represent the bonding sites with other structures.

[0469] [Chemical Formula 39]

[0470]

[0471] In the case where the resin composition of the present invention contains the structure represented by formula (1), it is acceptable as long as it is contained in the solid components of the resin composition. For example, the structure represented by formula (1) may be contained in the structure of a specific resin, or the resin composition may contain a compound that contains the structure represented by formula (1) but is different from the above-mentioned resin (hereinafter also referred to as "specific compound"). Furthermore, the resin composition may contain a resin having the structure represented by formula (1) and also contain a specific compound.

[0472] It is believed that when the resin composition of the present invention comprises the structure represented by formula (1) and contains a nitrogen-containing heterocyclic compound, the nitrogen-containing heterocyclic compound, acting as a rust inhibitor, is uniformly distributed at the interface between copper and polyimide through the interaction of a specific structure with the nitrogen-containing heterocyclic compound (especially 8-azaadenine), thereby uniformly suppressing copper corrosion. In particular, when a specific resin has an imide ring structure, the imide ring structure in the specific resin, the specific structure, and the nitrogen-containing heterocyclic compound form multi-point hydrogen bonds, thereby enabling the nitrogen-containing heterocyclic compound to be uniformly dispersed in the resin film. Furthermore, the carbonyl group in the imide ring can also interact with copper, so it is believed that the nitrogen-containing heterocyclic compound, which functions as a rust inhibitor, is uniformly distributed at the interface between copper and polyimide. Therefore, it is believed that copper corrosion can be uniformly suppressed, and short circuits can be prevented.

[0473] [R] 1 and R 2 ]

[0474] In equation (1), R 1 and R 2Each phenyl group independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group that can be substituted with an alkyl group having 1 to 10 carbon atoms. The saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms is more preferably isopropyl or cyclohexyl. The alkyl group having 1 to 10 carbon atoms that can be a substituent in the above-mentioned phenyl group is preferably a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms, more preferably a branched alkyl group having 3 to 6 carbon atoms, and even more preferably isopropyl. The number of substituents in the above-mentioned phenyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.

[0475] R 1 and R 2 Each is preferably isopropyl, cyclohexyl, or a phenyl group that can be substituted with isopropyl.

[0476] [X] 1 ]

[0477] In equation (1), X 1 It represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

[0478] [L] 1 ]

[0479] In equation (1), L 1 It represents -C(=O)- or -S(=O)2-, preferably -C(=O)-.

[0480] [Ring structure]

[0481] In equation (1), R 1 R 2 , bonded to * 1 Structure and bonding to * 2 At least two of the components in the structure can bond together to form a ring structure. Examples of the formed ring structures include hydantoin rings and N-acylimidazolium rings, but are not limited to these.

[0482] Furthermore, in this invention, R 1 R 2 , bonded to * 1 Structure and bonding to * 2 The method in which no ring structure is formed is also one of the preferred methods.

[0483] [Formula (X-1)]

[0484] In the case where the resin composition of the present invention contains the structure represented by formula (1), the structure represented by formula (1) is preferably contained as a group represented by the following formula (X-1).

[0485] [Chemical Formula 40]

[0486]

[0487] In equation (X-1), R 1 R 2 X 1 and L 1 respectively with R in equation (1) 1 R 2 X 1 and L 1 The meanings are the same, and the preferred selection methods are also the same.

[0488] In equation (X-1), R 3 The symbol represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Examples of aliphatic hydrocarbon groups or aromatic hydrocarbon groups include the aforementioned R. 1 Examples of functional groups.

[0489] Specific examples of the group represented by formula (X-1) can be given below, but are not limited to these groups. In the following formulas, * indicates a bonding site with other structures.

[0490] [Chemical Formula 41]

[0491]

[0492] 〔content〕

[0493] When the resin composition of the present invention comprises the structure represented by formula (1), the molar amount of the structure represented by formula (1) relative to the total solid content of the resin composition of the present invention is 0.005 to 0.5 mmol / g. The above molar amount is preferably 0.01 mmol / g to 0.3 mmol / g, more preferably 0.015 to 0.2 mmol / g.

[0494] It is believed that if the molar content is below the upper limit, it is easy to obtain a cured film that exhibits excellent storage stability, such as the ability to inhibit the cyclization of polyimide precursors and the ability to inhibit the breaking of the main chain of a specific resin.

[0495] The method for determining the above-mentioned content is not particularly limited; for example, the determination method in the examples described later can be cited.

[0496] The method for determining the total solids content is not particularly limited. For example, the method described in the examples below can be used, or a method for drying the resin composition by setting the temperature and pressure while confirming that no volatile components other than the solvent are present can be used. The method for determining the total solids content is not limited to any method that can determine the content of components other than the solvent in the resin composition that constitute the total solids content.

[0497] The above content is the molar amount of the structure represented by formula (1) relative to the total solids of the resin composition. For example, in the case where the resin composition contains a resin having the structure represented by formula (1) and contains a specific compound, the above content is the sum of the structure represented by formula (1) contained in the resin and the structure represented by formula (1) contained in the specific compound.

[0498] <Specific Compound>

[0499] The resin composition of the present invention may contain a compound (specific compound) having the structure represented by the above formula (1) and different from the above resin.

[0500] The specific compound includes the structure represented by formula (1), but is not particularly limited otherwise, and is preferably a low molecular weight compound.

[0501] Specifically, the molecular weight of the particular compound is preferably 75 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500.

[0502] The preferred compound is the one represented by the following formula (3-1).

[0503] [Chemical Formula 42]

[0504]

[0505] In equation (3-1), R 1 R 2 X 1 and L 1 respectively with R in equation (1) 1 R 2 X 1 and L 1 The meanings are the same, and the preferred selection methods are also the same.

[0506] In equation (3-1), R 3 R in equation (X-1) 3 The meanings are the same, and the preferred selection methods are also the same.

[0507] In equation (3-1), R 4 It is a monovalent organic group, preferably a hydrocarbon group.

[0508] The hydrocarbon group described above is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably an aromatic hydrocarbon group.

[0509] The aliphatic hydrocarbon group mentioned above is preferably a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group with 3 to 10 carbon atoms.

[0510] The aromatic hydrocarbon group mentioned above is preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, more preferably a phenyl or naphthyl group, and even more preferably a phenyl group.

[0511] R 4 The monovalent organic group in it can have substituents. Examples of substituents include alkyl, alkoxycarbonyl, and aryloxycarbonyl groups.

[0512] Among these, as R 4 Preferably, it is phenyl, alkylphenyl, or alkoxycarbonylphenyl, and more preferably phenyl, tert-butylphenyl, or alkoxycarbonylphenyl with 1 to 4 carbon atoms.

[0513] In equation (3-1), R 1 R 2 R 3 and R 4 At least two of the atoms can bond together to form a ring structure. Examples of the formed ring structures include hydantoin rings and N-acylimidazolium rings, but are not limited to these.

[0514] Furthermore, in this invention, R 1 R 2 R 3 and R 4 The method that does not form a ring structure is also one of the preferred methods.

[0515] The following are specific examples of preferred embodiments of certain compounds, but the invention is not limited to these.

[0516] [Chemical Formula 43]

[0517]

[0518] [Chemical Formula 44]

[0519]

[0520] When the resin composition contains a specific compound, the molar amount of the structure represented by formula (1) relative to the total solid content of the resin composition can be appropriately adjusted to an amount that reaches the above-mentioned range.

[0521] Furthermore, when the resin composition contains a specific compound, for example, its content relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5.0% by mass.

[0522] A specific compound may be used alone or in combination with two or more compounds. When two or more compounds are used together, it is preferable that their total amount is within the range described above.

[0523] <Urea compounds, carbodiimide compounds, isourea compounds>

[0524] From the viewpoint of elongation at break and adhesion to metal or resin layers, the resin composition of the present invention may contain at least one compound selected from the group consisting of urea compounds, carbodiimide compounds and isourea compounds (hereinafter also referred to as "urea compounds, etc.").

[0525] Examples of urea compounds include those represented by the following formula (UR-1), examples of carbodiimide compounds include those represented by the following formula (UR-2), and examples of isourea compounds include those represented by the following formula (UR-3).

[0526] [Chemical Formula 45]

[0527]

[0528] In formula (UR-1), formula (UR-2), or formula (UR-3), R 11 and R 12 Each of the following groups independently represents an aliphatic hydrocarbon group with 1 to 7 carbon atoms that can have substituents: R 21 and R 22 Each of the following groups independently represents an aliphatic hydrocarbon group with 1 to 7 carbon atoms that can have substituents: R 31 and R 32 Each of the following groups independently represents an aliphatic hydrocarbon group with 1 to 7 carbon atoms that can have substituents: R 33 It indicates an aliphatic hydrocarbon group with 1 to 7 carbon atoms that can have substituents.

[0529] In equation (UR-1), R 11 and R 12 Each and every one of the following is preferred to be an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having at least one substituent selected from the group consisting of primary amine salt structure, secondary amine salt structure, tertiary amine salt structure and quaternary ammonium group as a substituent, more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[0530] As R 11 and R12 The unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and even more preferably ethyl, isopropyl, tert-butyl or cyclohexyl.

[0531] In equation (UR-1), R 11 and R 12 Each can be an aliphatic hydrocarbon group with 2 to 7 carbon atoms, having at least one substituent selected from the group consisting of hydroxyl, alkoxy, thiol, and alkylthio groups.

[0532] The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have 2 or more of the above-mentioned substituents, but preferably only 1 of the above-mentioned substituents.

[0533] In equation (UR-2), R 21 and R 22 Each can be independently represented as an aliphatic hydrocarbon group with 1 to 7 carbon atoms that can have substituents.

[0534] In equation (UR-2), R 21 and R 22 Preferably, it is an aliphatic hydrocarbon group with 1 to 7 unsubstituted carbon atoms or an aliphatic hydrocarbon group with 1 to 7 carbon atoms having an amino or quaternary ammonium group as a substituent, more preferably an aliphatic hydrocarbon group with 1 to 7 unsubstituted carbon atoms.

[0535] In equation (UR-2), R 21 and R 22 The preferred embodiments of the above-mentioned unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms or aliphatic hydrocarbon groups having 1 to 7 carbon atoms with the above-mentioned substituents are respectively related to R. 11 and R 12 The method is the same as shown in the description.

[0536] In equation (UR-3), R 31 and R 32 Preferably, it is an aliphatic hydrocarbon group with 1 to 7 unsubstituted carbon atoms or an aliphatic hydrocarbon group with 1 to 7 carbon atoms having an amino or quaternary ammonium group as a substituent, more preferably an aliphatic hydrocarbon group with 1 to 7 unsubstituted carbon atoms.

[0537] In equation (UR-3), R 31 and R 32 The preferred embodiments of the above-mentioned unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms or aliphatic hydrocarbon groups having 1 to 7 carbon atoms with the above-mentioned substituents are respectively related to R. 11 and R 12 The method is the same as shown in the description.

[0538] In equation (UR-3), R 33 The term refers to an aliphatic hydrocarbon group having 1 to 7 carbon atoms that may have substituents, preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0539] In equation (UR-3), R is... 33 Preferably, it is methyl, ethyl, propyl, isopropyl, butyl, or tert-butyl, and more preferably ethyl.

[0540] Specific examples of urea compounds include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, etc., but are not limited to these.

[0541] The total content of urea compounds, etc., relative to 100 parts by weight of a specific resin is preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 8.0 parts by weight, and even more preferably 1.0 to 6.0 parts by weight.

[0542] Urea compounds can be used alone or in combination with two or more. When two or more alkalis are used in combination in an alkaline treatment solution, it is preferable that the total content of these compounds is within the range described above.

[0543] <Polymerizing compounds>

[0544] The resin composition of the present invention preferably contains a polymerizable compound.

[0545] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0546] [Free radical cross-linking agent]

[0547] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0548] Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, these free radical polymerizable groups contain olefinically unsaturated bonds. Examples of such olefinically unsaturated groups include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0549] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0550] 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.

[0551] 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.

[0552] 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 compounds having three or more of the above-mentioned olefinic unsaturated bonds.

[0553] 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.

[0554] 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 and 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 sulfonamide groups with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids. Furthermore, it is also preferable to use 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, and substitution reactions of unsaturated carboxylic acid esters or amides with leaving substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as another example, compounds that can be replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can also be used instead of the aforementioned unsaturated carboxylic acids. 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.

[0555] 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.

[0556] Preferred free radical crosslinking agents, other than those mentioned above, include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0557] As a free radical crosslinking agent, preferred are dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)), and structures formed by bonding these (meth)acryloyl groups via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0558] 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); DPCA-60, a hexafunctional acrylate with six pentenoxy groups; TPA-330, a trifunctional acrylate with three isobutyleneoxy groups (all manufactured by Nippon Kayaku Co., Ltd.); UAS-10 and UAB-140, polyurethane oligomers (all manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NKEster M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.); and DPHA-40H (Nippon Kayaku Co., Ltd.). Manufactured by 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.

[0559] As free radical crosslinking agents, polyurethane acrylates as described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, or polyurethane compounds with an ethylene oxide backbone as described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418 are also preferred. Compounds with an intramolecular amino or thioether structure as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 can also be used as free radical crosslinking agents.

[0560] 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 pentaerythritol or dipentaerythritol. Examples of commercially available products include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD., such as M-510 and M-520.

[0561] 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.

[0562] As a free radical crosslinking agent, it is also preferred to be a free radical crosslinking agent having at least one of the groups selected from urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U").

[0563] Including crosslinking agent U in the resin composition can sometimes improve chemical resistance, resolution, etc.

[0564] As a crosslinking agent U, compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064 can be cited. This content is incorporated into this specification.

[0565] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylates or acrylates.

[0566] 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, 3-methyl-1,5-pentylene glycol diacrylate, and 1,6-hexanediol diacrylate can be used. 1,6-Hexanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified dimethacrylate of isocyanuric acid, EO-modified dimethacrylate of isocyanuric acid, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be used in combination as needed.

[0567] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, and the molecular weight of the polyethylene glycol chain is around 200.

[0568] 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 atmospheric pressure are also preferred.

[0569] 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.

[0570] 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.

[0571] The free radical crosslinking agent can be used alone or in combination with two or more. When using two or more in combination, it is preferable that their total amount is within the range mentioned above.

[0572] [Other crosslinking agents]

[0573] The resin composition of the present invention preferably also contains other crosslinking agents that are different from the free radical crosslinking agents described above.

[0574] 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 in the composition or their reaction products by the photosensitive acid generator or photobase generator mentioned above. More preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds in the composition or their reaction products by the action of acid or base.

[0575] The acid or base mentioned above is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure process.

[0576] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0577] The content of other crosslinking agents 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 particularly preferably 1.0 to 10% by mass. The other crosslinking agents may be only one type or may be two or more types. When two or more other crosslinking agents are contained, it is preferable that their total content falls within the above range.

[0578] <Alkali generating agent>

[0579] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of generating alkali through physical or chemical action. Preferred alkali-generating agents include thermal alkali-generating agents and photo-alkali-generating agents.

[0580] By including a thermal alkali generating agent in the resin composition, such as one that can promote the cyclization reaction of the precursor by heating, the mechanical properties or chemical resistance of the cured product are improved, for example, the performance of the interlayer insulating film used as a redistribution layer in a semiconductor package is improved.

[0581] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases produced by a base-generating agent include secondary and tertiary amines.

[0582] The base-generating agent is not particularly limited, and known base-generating agents can be used. Examples of known base-generating agents include, for instance, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamate compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imine onium salts, pyridinium onium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0583] Specific examples of nonionic base generating agents include the compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0584] The following compounds can be cited as base-generating agents, but are not limited to these.

[0585] [Chemical Formula 46]

[0586]

[0587] The molecular weight of the nonionic alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0588] Specific preferred compounds for generating ionic bases include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0589] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[0590] [Chemical Formula 47]

[0591]

[0592] Specific examples of imine onium salts include the following compounds, but are not limited to these.

[0593] [Chemical Formula 48]

[0594]

[0595] Furthermore, from the viewpoint of storage stability and the generation of alkali during curing due to deprotection, an amine with the amino group protected by a tert-butoxycarbonyl group is preferred as an alkali generating agent.

[0596] Examples of amine compounds protected by a tert-butoxycarbonyl group include, for example, 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, and α-[2-(methylamino)ethyl]benzyl Compounds containing alcohols, diethanolamine, diisopropanolamine, 3-pyrrolidone, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanediol 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, wherein the amino group is protected by a tert-butoxycarbonyl group, but not limited to these.

[0597] 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.

[0598] 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-mentioned range.

[0599] <Solvent>

[0600] The resin composition of the present invention preferably contains a solvent.

[0601] 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.

[0602] Examples of esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, 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). Ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-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.

[0603] Examples of ethers include, for instance, 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, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0604] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0605] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0606] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0607] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0608] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolium ketone.

[0609] 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.

[0610] Regarding solvents, from the viewpoint of improving the properties of the coating surface, it is preferable to mix two or more forms.

[0611] 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, 3-butoxy-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-glucanone, and dihydroL-glucanone, 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 the solvent to these combined solvents is also a preferred method of the present invention.

[0612] 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, the upper limit of the above content is not particularly limited and 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.

[0613] 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.

[0614] From the viewpoint of coatability, the solvent content is preferably such that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating and the coating method. When two or more solvents are contained, it is preferable that their total content is within the above range.

[0615] <Metal Adhesion Improver>

[0616] 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 alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0617] [Silane coupling agent]

[0618] As silane coupling agents, examples include 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 formula, Me represents methyl and Et represents ethyl. Furthermore, R can be a structure derived from the blocking agent in the blocked 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.).

[0619] [Chemical Formula 49]

[0620]

[0621] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3- ... Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0622] Furthermore, as a silane coupling agent, compounds of oligomer type having multiple alkoxysilyl groups can also be used.

[0623] Examples of this type of oligomer include compounds containing repeating units represented by the following formula (S-1).

[0624] [Chemical Formula 50]

[0625]

[0626] 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.

[0627] R S1 The preferred structure includes a polymerizable group. Examples of polymerizable groups include groups having an olefinic unsaturated bond, epoxy groups, oxobutyl 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.

[0628] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[0629] n represents an integer from 0 to 2, preferably 1.

[0630] Here, the repeating units represented by multiple formulas (S-1) contained in the oligomer type of compound may have the same structure.

[0631] Here, among the repeating units represented by the multiple formulas (S-1) contained in the oligomer type compound, it is preferred that at least one has n=1 or 2, more preferably at least two have n=1 or 2, and even more preferably at least two have n=1.

[0632] As for this type of oligomer compound, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0633] [Aluminum-based adhesives]

[0634] Examples of aluminum-based adhesives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate diisopropoxyaluminum.

[0635] As other metal adhesion improvers, 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.

[0636] 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. The metal adhesion modifier may be only one type or two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0637] <Light Absorber>

[0638] The resin composition of the present invention preferably also contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.

[0639] 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.

[0640] Furthermore, as a light absorber, a compound containing the following structure is preferred.

[0641] [Chemical Formula 51]

[0642]

[0643] The content of light absorber relative to the total solids content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0644] <Nitrogen-containing heterocyclic compounds>

[0645] The resin composition preferably further comprises a nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound acts as a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, it can effectively inhibit the migration of metal ions from the metal layer (or metal wiring) into the film.

[0646] Furthermore, it is believed that nitrogen-containing heterocyclic compounds, especially 8-azaadenine, can form hydrogen bonds with carboxylic acid groups in specific resins having the aforementioned esterification rates, thereby inhibiting the formation of copper oxide films. Specifically, it is believed that when the esterification rate of the resin is 99.90% or less, the nitrogen-containing heterocyclic compounds can be effectively distributed near the copper wiring through interaction with the carboxylic acid groups of the resin. Moreover, when the esterification rate of the resin is 90.00% or more, it is possible to prevent copper corrosion based on carboxylic acid groups from exceeding the rust-preventing effect of the nitrogen-containing heterocyclic compounds.

[0647] There are no particular limitations on the nitrogen-containing heterocyclic compound, but nitrogen-containing aromatic heterocyclic compounds are preferred. Examples include compounds with pyrrole rings, imidazole rings, oxazole rings, thiazole rings, pyrazole rings, isoxazole rings, isothiazole rings, tetrazolium rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, piperazine rings, morpholine rings, triazine rings, or compounds having nitrogen-containing fused rings (purine rings, etc.). 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, tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole, and 8-azaadenine are preferred.

[0648] In these, the resin composition preferably contains 8-azaadenine.

[0649] When the resin composition contains a nitrogen-containing heterocyclic compound, the content of the nitrogen-containing heterocyclic compound relative to the total solid content of the resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0650] The nitrogen-containing heterocyclic compound can be only one type or two or more types. When there are two or more nitrogen-containing heterocyclic compounds, their total number is preferably within the range described above.

[0651] <Other migration inhibitors>

[0652] The resin composition may contain other migration inhibitors.

[0653] Other migration inhibitors include compounds having a furan ring, compounds having a thiophene ring, thioureas and compounds having a sulfonamide group, hindered phenolic compounds, salicylic acid derivatives, hydrazide derivatives, rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0654] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0655] When the resin composition contains other migration inhibitors, the content of the other migration inhibitors 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.

[0656] There may be only one other migration inhibitor, or there may be two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the range described above. Furthermore, the total number of nitrogen-containing heterocyclic compounds and other migration inhibitors is preferably within the range described above.

[0657] <Organotitanium compounds>

[0658] By incorporating organotitanium compounds into the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0659] As usable organotitanium compounds, examples include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0660] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0661] I) Titanium chelates: Since the resin composition has excellent storage stability and can obtain good cured patterns, titanium chelates having two or more alkoxy groups are preferred. Specific examples are bis(triethanolamine)diisopropoxy titanium, bis(n-butoxy)bis(2,4-pentanedione) titanium, diisopropoxybis(2,4-pentanedione) titanium, diisopropoxybis(tetramethylheptanedione) titanium, diisopropoxybis(ethyl acetoacetate) titanium, etc.

[0662] 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.

[0663] III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0664] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzene sulfonate) isopropoxy titanium, etc.

[0665] V) Titanium oxide compounds: such as bis(pentanedione) titanium oxide, bis(tetramethylheptadecanoic acid) titanium oxide, phthalocyanine titanium oxide, etc.

[0666] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0667] VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0668] From the viewpoint of better chemical resistance, at least one compound selected from the group consisting of I) titanium chelates, 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.

[0669] Furthermore, the compound may preferably contain a titanium complex, or alternative to an organotitanium compound, and examples of titanium complex compounds may include compounds represented by the following formula (T-1).

[0670] [Chemical Formula 52]

[0671]

[0672] 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 11R 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 R are groups that independently contain the structure represented by the following formula (T-2). 3 X are groups that independently contain the structure represented by the following formula (T-2). A Each can be an oxygen atom or a sulfur atom, independently.

[0673] [Chemical Formula 53]

[0674]

[0675] 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.

[0676] In formula (T-1), from the viewpoint of the preservation stability of the composition, M is preferably titanium.

[0677] In formula (T-1), the arrangement of l1 and l2 being 0 is also one of the preferred embodiments of the present invention.

[0678] In formula (T-1), m is preferably 2 or 4, more preferably 2.

[0679] In formula (T-1), n ​​is preferably 1 or 2, more preferably 1.

[0680] Here, in equation (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2 or 4.

[0681] In equation (T-1), from the perspective of the stability of a specific metal complex, R 11 Preferably, it is a substituted or unsubstituted cyclopentadienyl group.

[0682] 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.

[0683] 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.

[0684] As R 12 The hydrocarbon group in the form can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aromatic hydrocarbon group.

[0685] 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.

[0686] 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.

[0687] As R 12 The substituents in R are preferably monovalent substituents, such as halogen atoms. 12 In the case of aromatic hydrocarbon groups, alkyl groups can be used as substituents.

[0688] 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.

[0689] 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.

[0690] 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.

[0691] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, preferably at least one representation of -C(-*)=, more preferably at least two representations of -C(-*)=.

[0692] As specific examples of compounds represented by formula (T-1), compounds belonging to I-1 and I-2 in the examples can be cited, but are not limited to these.

[0693] When an organotitanium compound is included, its content relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and even more preferably 0.1 to 2 parts by weight. 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.

[0694] <Antioxidants>

[0695] The cured product of the present invention may contain antioxidants.

[0696] In this invention, an antioxidant refers to a compound that has the function of preventing metal oxidation, such as phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound well-known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds can be mentioned. Preferably, it is a compound having a substituent at the position (ortho) adjacent to the phenolic hydroxyl group. As a substituent, it is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, the antioxidant is also preferably a compound having both a phenolic group and a phosphite group within the same molecule.

[0697] It is believed that antioxidants can prevent the oxidation of metals, thus curing products containing antioxidants have excellent adhesion.

[0698] Furthermore, it is believed that antioxidants can inhibit the polymerization of polymerizable compounds during the storage of resin compositions, thus the storage stability of resin compositions containing antioxidants and the resolution of the obtained cured products are excellent.

[0699] As an antioxidant, it is preferred to have an isocyanuric acid backbone, and more preferably a hindered phenolic compound having an isocyanuric acid backbone.

[0700] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0701] [Chemical Formula 54]

[0702]

[0703] In general formula (3), R 5 R represents an alkyl group having one or more hydrogen atoms or carbon atoms. 6 R represents an alkylene group having 1 or more carbon atoms, an alkylene carbonyl group having 2 or more carbon atoms, or an alkylene carbonyloxy group having 2 or more carbon atoms. 7 It represents a 1- to 4-valent organic group containing at least one of an alkylene group with 2 or more carbon atoms, an O atom, and a N atom, where i represents an integer from 1 to 4, j represents an integer from 0 to 4, i+j is an integer from 1 to 4, and k represents an integer from 1 to 4.

[0704] By including compounds represented by general formula (3), in addition to inhibiting the oxidation of metals, the oxidative degradation of aliphatic groups or phenolic hydroxyl groups of resins can also be inhibited.

[0705] R 5 Preferably, it is an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0706] In R 6When the alkylene group is alkylene, it is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.

[0707] In R 6 When the carbonyl group is alkylene carbonyl, it is preferably an alkylene carbonyl group with 3 to 6 carbon atoms, and more preferably a methyl group. Furthermore, the carbonyl group is preferably present in relation to R. 7 The bonding sites.

[0708] In R 6 In the case of an alkylene carbonyl group, it is preferably an alkylene carbonyl group with 3 to 4 carbon atoms, and more preferably a methyl group.

[0709] As R 7 Examples of such groups include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl group, alkoxysilyl group, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and groups formed by combining these groups, which may further have substituents.

[0710] From the viewpoint of developability or metal adhesion, it is preferable to have an alkyl ether group, -NH-, or an isocyanurate ring, and from the viewpoint of interaction with the resin and metal adhesion based on the formation of metal complexes, it is more preferably an isocyanurate ring.

[0711] i is preferably 1 or 2, more preferably 1.

[0712] j is preferably an integer from 0 to 3, and more preferably an integer from 0 to 2.

[0713] k is more preferably an integer from 2 to 4.

[0714] Regarding the compounds represented by the following general formula (3), the following compounds can be cited as examples, but are not limited to the following structures.

[0715] [Chemical Formula 55]

[0716]

[0717] [Chemical Formula 56]

[0718]

[0719] [Chemical Formula 57]

[0720]

[0721] [Chemical Formula 58]

[0722]

[0723] Other antioxidants include phenolic compounds, quinone compounds, amino compounds, N-oxygen free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0724] Specific examples of these compounds include those described in paragraph 0310 of International Publication No. 2021 / 112189, hydroquinone, catechol, p-methoxyphenol, 2-nitroso-1-naphthol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo 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.

[0725] Furthermore, phosphorus-based antioxidants are preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphazene-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphazene-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants. Moreover, the compositions of the present invention can contain potential antioxidants as needed. Compounds that function as potential antioxidants include those whose antioxidant sites are protected by a protecting group and which, upon heating at 100–250°C or at 80–200°C in the presence of an acid / base catalyst, detach the protecting group and thus function as antioxidants. Examples of potential antioxidants include compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219. Commercially available examples of potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

[0726] The content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of a specific resin. By setting the addition amount to 0.1 parts by weight or more, it is easy to obtain the effect of improved elongation properties or adhesion to metal materials, even under high temperature and high humidity environments. Furthermore, by setting the addition amount to 10 parts by weight or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above-mentioned range.

[0727] <Polymerization Inhibitor>

[0728] 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.

[0729] Specific compounds that can be used as polymerization inhibitors include those described in paragraph 0310 of International Patent Publication No. 2021 / 112189, hydroquinone, catechol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is included in this specification.

[0730] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid 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.

[0731] The polymerization inhibitor can be one type or two or more types. When there are two or more polymerization inhibitors, it is preferable that their total number is within the range described above.

[0732] <Other Additives>

[0733] The resin composition of the present invention may contain various additives as needed within the range that achieves the effects of the present invention, such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, photoacid generators, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the physical properties of the membrane 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 incorporated, 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.

[0734] [surfactants]

[0735] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0736] 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, and the uniformity of the coating thickness or the liquid-saving properties can be further improved. 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.

[0737] As fluorinated surfactants, compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which is incorporated herein by reference, can be cited.

[0738] As a fluorinated surfactant, a fluorinated polymer compound can also be preferably used, which comprises: repeating units from a (meth)acrylate compound having fluorine atoms; and repeating units from a (meth)acrylate compound having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propyleneoxy groups), for example, the following compounds can be cited.

[0739] [Chemical Formula 59]

[0740]

[0741] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0742] 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 DIC Corporation.

[0743] 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. Fluorinated surfactants with fluorine content in this range are effective from the viewpoint of uniform coating thickness and liquid-saving properties, and also have good solubility in the composition.

[0744] 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.

[0745] Surfactants can be used in single-component or in combination of two or more types.

[0746] 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.

[0747] [Inorganic particles]

[0748] 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.

[0749] 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.

[0750] 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.).

[0751] In cases where the above measurements are difficult to perform, they can also be determined by centrifugal sedimentation light transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0752] 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.

[0753] <Characteristics of the Resin Composition>

[0754] The viscosity of the resin composition of the present invention at 23°C can be adjusted by adjusting the concentration of the solid components in 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 use as an insulating film for rewiring. 2 When the speed is below a certain value, a coating film with excellent surface properties can be obtained.

[0755] <Restrictions on the Contents of Substances in Resin Compositions>

[0756] 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.

[0757] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[0758] 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 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.

[0759] Furthermore, as a method for reducing unintentionally contained metallic 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.

[0760] Considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion resistance, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The content of substances 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.

[0761] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0762] As a container for the resin composition of the present invention, conventionally known containers can be used. For the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layered bottles with the inner wall composed of six layers of six different resins or bottles with the six resins formed into a seven-layer structure are also preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0763] <Cureds of Resin Compositions>

[0764] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0765] The cured product of the present invention is a cured product formed by curing a resin composition.

[0766] The curing of the resin composition is preferably carried out by heating, with a heating temperature more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The morphology of the cured resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product is preferably in film form. The shape of the cured product can also be selected by patterning the resin composition, depending on applications such as forming a protective film on a wall surface, forming viaholes for conduction, adjusting impedance or electrostatic capacitance or internal stress, or providing heat dissipation. The film thickness of the cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0767] 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, the 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.

[0768] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0769] <Characteristics of cured resin compositions>

[0770] 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.

[0771] 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.

[0772] 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.

[0773] <Preparation of Resin Compositions>

[0774] 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.

[0775] Examples of mixing methods include mixing based on stirring blades, mixing based on ball mills, and mixing by rotating a tank.

[0776] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0777] For the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration using a filter is preferred. 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. Examples of filters include those described in paragraph 0287 of International Publication No. 2023 / 190064. The above is incorporated herein by reference.

[0778] (Method for manufacturing solidified products)

[0779] 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.

[0780] 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.

[0781] 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.

[0782] 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.

[0783] The following is a detailed explanation of each process.

[0784] <Membrane Formation Process>

[0785] The resin composition of the present invention can be used in a film forming process applied to a substrate to form a film.

[0786] 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.

[0787] [Substrate]

[0788] 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, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any substrate formed of metal or substrate with a metal layer formed by plating, vapor deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). Semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred.

[0789] Alternatively, a bonding layer or oxide layer formed of hexamethyldisilazane (HMDS) or similar material can be provided on the surface of these substrates.

[0790] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[0791] 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.

[0792] As a substrate, for example, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0793] When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer composed of cured material) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0794] As a method for applying a resin composition to a substrate, coating is preferred.

[0795] 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 are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are 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.

[0796] Furthermore, it is also possible to apply a method for transferring a coating film formed by pre-applying it to a pre-support body using the above-described application method onto a substrate.

[0797] 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 preferably used.

[0798] 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.

[0799] Alternatively, a pre-wetting process can be used: before applying the resin composition to the substrate, apply various solvents to the substrate to improve the wettability of the substrate, and then apply the resin composition.

[0800] <Drying Process>

[0801] After the film formation process (layer formation process), in order to remove the solvent, the above-mentioned membrane can be used in a process of drying the formed membrane (layer) (drying process).

[0802] 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.

[0803] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0804] 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.

[0805] <Exposure Process>

[0806] The above-mentioned film can be used in the exposure process of selectively exposing the film.

[0807] The method for manufacturing a cured material may include an exposure process that selectively exposes a film formed by a film forming process.

[0808] Selective exposure means exposing a portion of the film. Furthermore, by selective exposure, exposed areas (exposed areas) and unexposed areas (non-exposed areas) are formed on the film.

[0809] Regarding the exposure amount, it is not particularly limited as long as it is sufficient to cure the resin composition of the present invention, but preferably 50 to 10,000 mJ / cm², for example, when converted to exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[0810] The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0811] 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, and i-ray wavelengths), (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, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. 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.

[0812] The exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed, such as exposure using a photomask or exposure based on direct laser imaging.

[0813] <Post-exposure heating process>

[0814] The above-mentioned film can also be used in the process of heating after exposure (post-exposure heating process).

[0815] 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.

[0816] The post-exposure heating process can be performed after the exposure process and before the development process.

[0817] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0818] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0819] 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.

[0820] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0821] As a heating mechanism in the post-exposure heating process, it is not particularly limited and can use known heating plates, ovens, infrared heaters, etc.

[0822] 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.

[0823] <Developing Process>

[0824] The exposed film can also be used in the developing process to form patterns by developing with a developing solution.

[0825] 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.

[0826] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0827] Here, the development process that removes the non-exposed parts of the film is called negative development, and the development process that removes the exposed parts of the film is called positive development.

[0828] [Developing solution]

[0829] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0830] When the developing solution is an alkaline aqueous solution, examples of alkaline compounds that may be included in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Examples of alkaline compounds include those described in paragraph 0300 of International Publication No. 2023 / 190064. The above information is incorporated herein by reference. In the total mass of the developing solution, the content of the alkaline compound in the developing solution 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.

[0831] 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 herein by reference. Furthermore, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., are preferably examples of alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., are preferably examples of amides.

[0832] 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; a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred; and a developer containing cyclopentanone is especially preferred.

[0833] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content can also be 100% by mass.

[0834] The developer may further contain other ingredients.

[0835] Other components include, for example, well-known surfactants or well-known defoamers.

[0836] 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.

[0837] [Rinse solution]

[0838] 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.

[0839] 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.

[0840] 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.

[0841] 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.

[0842] 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.

[0843] The rinsing solution may further contain other ingredients.

[0844] Other components include, for example, well-known surfactants or well-known defoamers.

[0845] [Method for supplying flushing fluid]

[0846] 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.

[0847] 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.

[0848] 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.

[0849] As a method for supplying rinsing fluid in the rinsing process, methods such as continuously supplying rinsing fluid to the substrate, keeping the rinsing fluid in a substantially static state on the substrate, using ultrasound or the like to vibrate the rinsing fluid on the substrate, and combining these methods are all possible.

[0850] 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.

[0851] In the developing process, after treatment with developer or cleaning of the pattern with rinsing solution, a step may be included to bring the treatment solution into contact with the pattern. Furthermore, methods may be employed such as supplying the treatment solution before the developer or rinsing solution in contact with the pattern has completely dried.

[0852] <Heating Process>

[0853] 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 to heat the pattern obtained by the developing process described above.

[0854] 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.

[0855] 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.

[0856] During the heating process, resins such as polyimide precursors are cyclized to become resins such as polyimide.

[0857] Furthermore, crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed.

[0858] 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.

[0859] 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 like generated by the alkali generating agent.

[0860] Regarding the heating process, please refer to paragraphs

[0326] to

[0332] of International Publication No. 2023 / 190064, which is incorporated herein by reference.

[0861] <Metal Layer Formation Process>

[0862] 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 to form a metal layer on the pattern.

[0863] 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 for at least one of a heating step and a post-developing exposure step).

[0864] 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.

[0865] 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, electrolytic plating, 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 electrolytic plating can be cited. As a preferred method of plating, electrolytic plating using copper sulfate or copper cyanide plating solutions can be cited.

[0866] The thickness of the metal layer is preferably 0.01 to 50 μm in the thickest part, and more preferably 1 to 10 μm.

[0867] <Uses>

[0868] Examples of applications for the manufacturing method of the cured product of the present invention, or for the cured product itself, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress-relief films. Furthermore, examples include patterning end caps, 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 these applications, references can be made to publications such as SCIENCE AND TECHNOLOGY CO.,LTD. "High Functionalization and Application Technology of Polyimides," April 2008; Masaaki Kakimoto (ed.); CMC Technical Library "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association (ed.), "Latest Polyimide Fundamentals and Applications," NTS Inc., August 2010.

[0869] 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 electronic devices, especially microelectronic devices.

[0870] (Laminated bodies and methods for manufacturing laminated bodies)

[0871] The laminate of the present invention refers to a structure having multiple layers composed of the cured material of the present invention.

[0872] A laminate is a laminate consisting of two or more layers composed of a cured material, or it can be a laminate consisting of three or more layers.

[0873] In the above-described laminate, at least one of the two or more layers composed of the above-described cured material is a layer composed of 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 composed of the cured material included in the above-described laminate are layers composed of the cured material of the present invention.

[0874] 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.

[0875] The laminate of the present invention preferably comprises two or more layers made of cured material, and a metal layer is included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer forming process described above.

[0876] 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 composed of the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0877] As an example of the aforementioned laminate, a laminate comprising at least the following layer structure is preferably provided, wherein the layer structure is formed by sequentially stacking three layers: a layer composed of a first cured material, a metal layer, and a layer composed of a second cured material.

[0878] Both the layer composed of the first cured product and the layer composed of the second cured product are preferably layers composed of the cured products of the present invention. The resin composition of the present invention used to form the layer composed of the first cured product and the resin composition of the present invention used to form the layer composed of the second cured product may be the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0879] <Layering Process>

[0880] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0881] The lamination process includes a series of steps that sequentially perform at least one of the following on the surface of a pattern (resin layer) or a metal layer: (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. Alternatively, at least one of (a) the film formation step and (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 also appropriately include the aforementioned drying step, etc.

[0882] When 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.

[0883] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0884] 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.

[0885] The composition, shape, and film thickness of each of the above layers can be the same or different.

[0886] 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.

[0887] (Surface activation treatment process)

[0888] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer.

[0889] 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.

[0890] 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, surface activation treatment is performed on at least a portion of the metal layer, and more preferably on a portion or all of the area on the metal layer where the resin composition layer is formed. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on that surface can be improved.

[0891] Furthermore, the surface activation treatment is preferably performed on part or all of the exposed resin composition layer (resin layer). In this way, by performing surface activation treatment on the surface of the resin 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 is cured, such as during negative development, it is less susceptible to damage caused by the surface treatment, thus easily improving adhesion.

[0892] Surface activation treatment 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.

[0893] (Semiconductor devices and their manufacturing methods)

[0894] The present invention also discloses a semiconductor device comprising the cured material or laminate of the present invention.

[0895] 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.

[0896] As a specific example of using the resin composition of the present invention to form an interlayer insulating film for a redistribution 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.

[0897] Example

[0898] The following examples provide a further detailed description of the present invention. The materials, amounts, proportions, processing methods, and processing order shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" refer to mass measurements.

[0899] <Polymer Synthesis>

[0900] [Synthesis Example P-1: Synthesis of Resin (P-1)]

[0901] 93.07 g of 4,4'-oxophthalic dianhydride (ODPA) and 62.04 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were placed in a separating flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added. 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 allowed to cool naturally to room temperature and then allowed to stand for 16 hours.

[0902] Next, under ice cooling, while stirring, a solution containing 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes. Then, while stirring, a suspension of 96.0 g of 4,4'-diaminodiphenyl ether was added to 350 mL of γ-butyrolactone over 60 minutes. After stirring at room temperature for 2 hours, 30 mL of ethanol was added, and stirring continued for 1 hour. Then, 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration, thus yielding the reaction solution.

[0903] The obtained reaction solution was added to 3 L of ethanol, resulting in a precipitate composed of crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain 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 resin P-1.

[0904] pass 1 ¹H-NMR confirmed that resin P-1 contains a repeating unit represented by the following formula (P-1). The weight-average molecular weight, imidization rate, esterification rate, and amine value of resin P-1 are described in the table below. The symbols A and B added in parentheses represent the molar ratios of each structure, and their values ​​are described in the table below.

[0905] [Chemical Formula 60]

[0906]

[0907] [Synthetic Examples P-2 to P-52: Synthesis of Resins (P-2) to (P-52)]

[0908] The types and addition ratios of the acid anhydride and diamine used in synthetic example P-1 were appropriately modified, except that resins (P-2) to (P-52) were synthesized using the same method as resin (P-1). Furthermore, in the synthesis of resin (P-3), dicyclohexylcarbodiimide (DCC) was replaced with diisopropylcarbodiimide. Resins (P-2) to (P-52) are resins having repeating units represented by the following formulas (P-2) to (P-52), respectively. In the following structures, the symbols added in parentheses are values ​​recorded in the table below, indicating the molar ratio of each structure. 1 H-NMR spectroscopy determined the structure of each repeating unit. Furthermore, the weight-average molecular weight (Mw), imidization rate, esterification rate, acid value, and amine value of these resins are described in the table below.

[0909] Resins with the same structure but different Mw, imidization rate, esterification rate, acid value, amine value, and specific structure content can be obtained by appropriately changing the amount of raw materials added, reaction temperature, and reaction time.

[0910] [Chemical Formula 61]

[0911]

[0912] [Chemical Formula 62]

[0913]

[0914] [Chemical Formula 63]

[0915]

[0916] [Chemical Formula 64]

[0917]

[0918] [Chemical Formula 65]

[0919]

[0920] [Chemical Formula 66]

[0921]

[0922] [Chemical Formula 67]

[0923]

[0924] [Chemical Formula 68]

[0925]

[0926] [Chemical Formula 69]

[0927]

[0928] [Chemical Formula 70]

[0929]

[0930] [Chemical Formula 71]

[0931]

[0932] [Chemical Formula 72]

[0933]

[0934] [Chemical Formula 73]

[0935]

[0936] [Chemical Formula 74]

[0937]

[0938] [Chemical Formula 75]

[0939]

[0940] [Chemical Formula 76]

[0941]

[0942] [Chemical Formula 77]

[0943]

[0944] [Chemical Formula 78]

[0945]

[0946] [Chemical Formula 79]

[0947]

[0948] [Chemical Formula 80]

[0949]

[0950] [Chemical Formula 81]

[0951]

[0952] [Chemical Formula 82]

[0953]

[0954] [Chemical Formula 83]

[0955]

[0956] [Method for determining weight-average molecular weight]

[0957] The weight-average molecular weight of the resin was determined by the following method.

[0958] GPC measurements were performed using a high-speed GPC apparatus, HLC-8420GPC (manufactured by TOSOH CORPORATION), with a TSK guardcolumn Super AW-H (4.6 mm × 35 mm) as the guard column and two TSKgel Super AWM-H (4.6 mm × 150 mm) columns connected in series. A 0.01 mol / L lithium bromide NMP (N-methyl-2-pyrrolidone) solution was used as the eluent.

[0959] [Method for determining imidization rate]

[0960] The imidization rate of the resin was determined by the following method.

[0961] The resin was dissolved in γ-butyrolactone and diluted to 2,000 mPa·s, then applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer with the obtained resin layer was dried on a hot plate at 110°C for 5 minutes, resulting in a uniform resin layer with a film thickness of approximately 15 μm on the silicon wafer.

[0962] The resin layer was measured using Nicoleti S20 (manufactured by Thermo Fisher Scientific Inc.) and by the ATR method, within the measurement range of 4000–700 cm⁻¹. -1 The measurements were performed under conditions of 50 measurements. A 1380cm... -1 Nearby (1350-1450cm) -1 (In the case of multiple peaks, the peak with the highest intensity) is the peak height divided by 1500cm. -1 Nearby (1460-1550cm) -1 The imidization index A of the resin is determined by the peak height of the peak with the highest intensity when multiple peaks exist. For a film heated at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min, the imidization index B is calculated using the same method. The imidization rate of the resin is calculated by dividing the imidization index A by the imidization index B.

[0963] [Quantitative methods for esterification rate]

[0964] The esterification rate of the resins used in each embodiment or comparative example was determined by the following method.

[0965] 0.09 g of resin was dissolved in 0.9 g of DMSO-d6 (dimethyl sulfoxide-d6), and the results were determined. 1 H-NMR (Avance III HD manufactured by Bruker). The content of amyl ester structures (esterification rate) was calculated based on the ratio of the signal integral values ​​from the carboxylic acid structure to the signal from the ester structure, relative to the total molar amount of amyl acid structures and amyl ester structures in the resin.

[0966] [Quantitative methods for acid value]

[0967] The acid value of the resins used in each embodiment or comparative example was determined by the following method.

[0968] The assay solution was prepared by dissolving 0.30 g of resin in 80 mL of NMP and then adding 5 mL of water. The solution was titrated with a 0.01 N (0.01 mol / L) potassium hydroxide (KOH) aqueous solution, and the acid value was calculated based on the peaks in the pH range of 7.0–12.0.

[0969] The test results for each resin are recorded in the "Acid Value (mmol / g)" column of the table.

[0970] [Quantitative methods for amine value]

[0971] The amine value of the resins used in each embodiment or comparative example was determined by the following method.

[0972] The test solution was prepared by dissolving 0.60 g of resin in 50 mL of diethylene glycol dimethyl ether and then adding 10 mL of acetic acid. The neutralization point was determined by titrating the solution with 0.01 N (0.01 mol / L) perchloric acid in acetic acid, thereby determining the amine value of the resin.

[0973] The test results for each resin are recorded in the "Amine value (mmol / g)" column of the table.

[0974] [Quantitative methods for the content of specific structures]

[0975] The content of a specific structure represented by formula (1) in the resin composition was determined by the following method.

[0976] The resins used in the various examples or comparative examples were subjected to d6-DMSO. 1¹H-NMR analysis was used to quantify the content of the specific structure contained in the resin. In the components listed in Table 2, the total amount of components excluding the solvent was defined as the total solids content. Furthermore, assuming that the specific structure was contained only in the resin components, the content of the specific structure in the total solids content was calculated based on the relationship between the quantified content of the specific structure in the resin and the resin content in the total solids content.

[0977] The measurement results are recorded in the "Specific Structure Content (mmol / g)" column of the table.

[0978] [Table 1-1]

[0979]

[0980] [Table 1-2]

[0981]

[0982] <Examples and Comparative Examples>

[0983] The resin compositions used in the examples and comparative examples were obtained by mixing the components listed in Table 2 below. Specifically, the content of each component listed in Table 2 was set as the amount (parts by mass) recorded in the "parts by mass" column of each column of the table. The obtained resin compositions and the comparative compositions were pressure filtered using a polytetrafluoroethylene filter with a pore size of 0.8 μm. In addition, in Table 2, a "-" indicates that the composition does not contain the corresponding component.

[0984] The evaluation results of each resin composition are shown in Table 3.

[0985] [Table 2-1]

[0986]

[0987] [Table 2-2]

[0988]

[0989] [Table 2-3]

[0990]

[0991] [Table 2-4]

[0992]

[0993] [Table 2-5]

[0994]

[0995] [Table 2-6]

[0996]

[0997] [Table 2-7]

[0998]

[0999] [Table 3-1]

[1000]

[1001] [Table 3-2]

[1002]

[1003] [Resin]

[1004] • P-1 to P-52: The resins (P-1) to (P-52) synthesized above.

[1005] [Aniline compounds]

[1006] B-1: N-Phenylonamine

[1007] •B-2: Compounds with the following structure

[1008] •B-3: Compounds with the following structures

[1009] [Chemical Formula 84]

[1010]

[1011] [Polymerizing compounds]

[1012] •C-1: NK Ester 4G (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.)

[1013] •C-2: NK Ester TMPT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

[1014] • C-3: Dipentaerythritol hexaacrylate (manufactured by TCI)

[1015] • C-4: Compounds with the following structures

[1016] • C-5: Compounds with the following structures

[1017] [Chemical Formula 85]

[1018]

[1019] [Photopolymerization initiator]

[1020] •D-1: Compounds with the following structure

[1021] • D-2: IRGACURE OXE 01 (manufactured by BASF)

[1022] •D-3: Compounds with the following structure

[1023] •D-4: Compounds with the following structure

[1024] [Chemical Formula 86]

[1025]

[1026] [Sensitizer]

[1027] E-1: Compounds with the following structures

[1028] E-2: Compounds with the following structure

[1029] [Chemical Formula 87]

[1030]

[1031] [Antioxidants]

[1032] F-1: Compounds with the following structures

[1033] F-2: Compounds with the following structure

[1034] F-3: Compounds with the following structure

[1035] F-4: Compounds with the following structures

[1036] [Chemical Formula 88]

[1037]

[1038] [Metal adhesion improver]

[1039] • G-1: Compounds with the following structures

[1040] G-2: Compounds with the following structure

[1041] [Chemical Formula 89]

[1042]

[1043] [Nitrogen-containing heterocyclic compounds]

[1044] H-1: Compounds with the following structure

[1045] H-2: Compounds with the following structure

[1046] H-3: Compounds with the following structure

[1047] H-4: Compounds with the following structure

[1048] [Chemical Formula 90]

[1049]

[1050] [Metal complex]

[1051] • I-1: Compounds with the following structure (iPr represents isopropyl)

[1052] • I-2: Compounds with the following structure

[1053] [Chemical Formula 91]

[1054]

[1055] [Hot alkali generating agent]

[1056] J-1: Compounds with the following structure

[1057] J-2: Compounds with the following structure

[1058] J-3: Compounds with the following structure

[1059] [Chemical Formula 92]

[1060]

[1061] [Urea compounds]

[1062] U-1: 1,3-Dicyclohexylurea

[1063] U-2: 1,3-Diisopropylurea

[1064] [Solvent]

[1065] L-1: γ-valerolactone

[1066] L-2: Ethyl lactate

[1067] L-3: Dimethyl sulfoxide

[1068] L-4: γ-Butyrolactone

[1069] L-5: N-methyl-2-pyrrolidone

[1070] L-6: 3-Methoxy-N,N-Dimethylpropionamide

[1071] L-7: 3-Butoxy-N,N-Dimethylpropionamide

[1072] <Evaluation>

[1073] [Wafer surface linewidth uniformity]

[1074] First, the optimal exposure amount of the resin composition or comparative composition prepared in each embodiment or comparative example was determined by the following method.

[1075] A resin composition was spin-coated onto a silicon wafer with a copper thin layer on its surface. After drying at 110°C for 5 minutes to form a resin composition layer with a film thickness of 7 μm, a square via mask with a 7 μm pattern was used. An i-line stepper (Canon FPA-3000i5, NA=0.5, σ=0.7) was then used at 100–1500 mJ / cm². 2 Within the range of 50mJ / cm 2 The obtained resin composition layer was exposed at various intervals. Next, it was developed with cyclopentanone until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and then heated at 230°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min. The obtained pattern was analyzed using a length-measuring scanning electron microscope (SEM: Scanning Electron Microscope (Hitachi High-Tech Corporation, S-9380II)) to measure the via width at each exposure. The exposure at which the via width reached 7 μm was determined and taken as the optimal exposure (mJ / cm²) for each composition. 2 ).

[1076] Next, the linewidth stability was evaluated in the following manner.

[1077] A resin composition was spin-coated onto a silicon wafer with a copper thin layer on its surface. After drying at 110°C for 5 minutes, a resin composition layer with a thickness of 7 μm was formed. A square via mask with a 7 μm pattern was then used to expose the entire wafer surface using an i-line stepper (Canon FPA-3000i5, NA=0.5, σ=0.7) at the optimal exposure levels for each composition determined by the above method. Next, the wafer was developed with cyclopentanone until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and then heated at 230°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min.

[1078] The obtained pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope (Hitachi High-Tech Corporation, S-9380II)) at any 100 points on the wafer surface. The standard deviation was calculated, and the pattern was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Linewidth Uniformity" column of the table. A smaller standard deviation indicates less susceptibility to slight environmental differences within the wafer surface, resulting in higher mass production adaptability.

[1079] A: Standard deviation is less than 0.05μm

[1080] B: Standard deviation is greater than 0.05 μm and less than 0.10 μm

[1081] C: Standard deviation is greater than 0.10 μm and less than 0.20 μm

[1082] D: Standard deviation is above 0.20μm

[1083] [Resolution Evaluation]

[1084] The resin compositions or comparative compositions prepared in the various examples or comparative examples were applied in a layered manner to the surface of the copper layer of a resin substrate on which a copper thin layer was formed by spin coating. After drying at 110°C for 5 minutes to form a resin composition layer with a film thickness of 4 μm, the obtained resin composition layer was subjected to a square via mask with a pattern of 0.5 to 10 μm at 0.5 μm intervals, and an i-line stepper (manufactured by Canon: FPA-3000i5, NA=0.5, σ=0.7) was used at 100 to 1500 mJ / cm². 2 Within the range of 50mJ / cm 2 Exposure was performed at intervals. Then, it was developed with cyclopentanone until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and then heated at 230°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min.

[1085] The opening pattern portion was cross-sectionally observed using a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) to determine the minimum opening mask diameter of the obtained cured product, and the evaluation was conducted according to the following evaluation criteria. The minimum opening mask diameter was set as the minimum value among the mask diameters used to form the opening pattern with at least one of the aforementioned exposure amounts. Furthermore, based on 800 mJ / cm²... 2The residual film percentage (%) is calculated by comparing the film thickness before and after development (film thickness after development / film thickness before development × 100). A residual film percentage of less than 80% is not optimal for forming the redistribution layer, regardless of the aperture mask size. The evaluation results are recorded in the "Resolution" column of the table.

[1086] (Evaluation Criteria)

[1087] A: The minimum aperture mask diameter is less than 3μm, and the residual film development rate is above 90%.

[1088] B: The minimum aperture mask diameter is greater than 3μm and less than 4μm, and the residual film rate is above 90%.

[1089] C: The minimum aperture mask diameter is greater than 4μm and less than 5μm, and the residual film rate is more than 90%.

[1090] D: Minimum aperture mask diameter exceeds 5μm, or residual film rate is less than 80%.

[1091] [Chemical resistance]

[1092] The resin compositions or comparative compositions prepared in the various examples or comparative examples were applied in layers onto a silicon wafer using a spin-coating method, and dried at 110°C for 5 minutes to form a resin composition layer with a film thickness of 15 μm. Next, the resin composition layer was subjected to exposure using a broadband exposure machine (manufactured by USHIO INC.: UX-1000SN-EH01) at 800 mJ / cm². 2 Full-area exposure was performed. Next, a heat treatment was conducted in a clean oven (Koyo manufactured, CLH-21) at 230°C for 1 hour under a N2 atmosphere to obtain a cured film of the resin composition or the comparative composition. The obtained cured film was impregnated in the following chemicals under the impregnation conditions described below, and the residual film rate (film thickness after impregnation / film thickness before impregnation × 100 (%)) was calculated based on the film thickness before and after impregnation. Evaluation was performed according to the following evaluation criteria, and the evaluation results were recorded in the "Chemical Resistance" column. It can be said that a higher residual film rate indicates better chemical resistance.

[1093] • Reagent: A 90:10 mixture of dimethyl sulfoxide (DMSO) and 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.

[1094] • Impregnation conditions: 30 minutes at 60°C

[1095] -Evaluation Criteria-

[1096] A: The residual film rate is over 95%.

[1097] B: The above residual film rate is 80% or more and less than 95%.

[1098] [Film-forming properties]

[1099] The resin compositions or comparative compositions prepared in each example or comparative example were spin-coated onto silicon wafers at 3000 rpm in an environment of 23°C and 50% humidity. The film surface was visually observed immediately after spin-coating and after standing for 5 minutes after spin-coating, and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Film Formation Properties" column of the table.

[1100] -Evaluation Criteria-

[1101] A: No white turbidity was observed in the film immediately after spin coating and after standing.

[1102] B: No cloudiness was observed in the membrane immediately after spin coating, but it was observed after standing.

[1103] [Maintaining stability]

[1104] The presence or absence of precipitation and the viscosity change rate of the resin compositions or comparative compositions prepared in each example or comparative example after being stored in a constant temperature bath at 23°C for 168 hours were evaluated according to the following evaluation criteria: |((viscosity after storage / viscosity before storage) × 100) - 100|. Viscosity was measured at 23°C using a TV-100E viscometer (manufactured by Toki Sangyo Co., Ltd.). The evaluation results are recorded in the "Storage Stability" column of the table.

[1105] (Evaluation Criteria)

[1106] A: The viscosity change rate is less than 2%, and no precipitation was observed.

[1107] B: The viscosity change rate is greater than 2% but less than 5%, and no precipitation was observed.

[1108] C: The viscosity change rate is greater than 5% and less than 10%, and no precipitation was observed.

[1109] Based on the above results, it can be seen that by using the resin composition of the present invention, the linewidth uniformity within the wafer surface is excellent. In contrast, it can be seen that when the resin does not have a specific structure or when the acid value of the resin exceeds a predetermined range, the linewidth uniformity within the wafer surface is significantly deteriorated.

[1110] Furthermore, by using the resin composition of the present invention, a cured film with excellent resolution, chemical resistance, film-forming properties, and storage stability can be obtained.

Claims

1. A resin composition comprising resin A and photosensitizer B, wherein, Resin A comprises an amide ester structure and an amide acid structure, and further comprises at least one structure selected from the group consisting of the structure represented by formula (AY1) and the structure represented by formula (DY1). The molar amount of the amamide ester structure in resin A is 90.00% to 99.90% relative to the total molar amount of the amamide acid structure and the amamide ester structure. The amine value of resin A is 0.0010–0.3000 mmol / g. In the formula, * indicates a bonding site with other structures. X is the group represented by formula (2a), where *1 to *4 represent the bonding sites with the carbonyl group, respectively. Y is any group selected from the following: 。 2. The resin composition according to claim 1, wherein it comprises a nitrogen-containing heterocyclic compound.

3. The resin composition according to claim 1, wherein, The resin composition comprises the structure represented by formula (1). In equation (1), R 1 and R 2 Each of the following groups independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group optionally substituted with an alkyl group having 1 to 10 carbon atoms: X 1 L represents an oxygen atom or a sulfur atom. 1 This represents -C (=O)- or -S (=O)2-, * 1 and* 2 Each independently represents a bonding site with other structures, R 1 R 2 , bonded to * 1 Structure and bonding to * 2 At least two optional bonds in the structure are bonded to form a ring structure. The resin composition contains 0.005 to 0.5 mmol / g of the structure represented by formula (1) relative to the total solids content.

4. The resin composition according to claim 1, wherein, Resin A includes the structure represented by the formula (1-dp-2d1). In the formula, * indicates the bonding site with other structures.

5. The resin composition according to claim 4, wherein, Resin A comprises at least one structure selected from the structure represented by formula (1-dp-V1-1) and the structure represented by formula (Y-V1-1). In the formula, * indicates the bonding site with other structures.

6. The resin composition according to any one of claims 1 to 5, wherein, The resin A contains an imide ring structure, and the imidization rate of resin A is 3-40%.

7. The resin composition according to any one of claims 1 to 5, wherein, The weight-average molecular weight of resin A is 15,000 to 40,000.

8. The resin composition according to any one of claims 1 to 5, wherein, The acid values ​​of the acid groups in resin A, whose neutralization point pH ranges from 7.0 to 12.0, range from 0.0010 to 0.3000 mmol / g.

9. The resin composition according to any one of claims 1 to 5, further comprising a titanium complex compound.

10. The resin composition according to any one of claims 1 to 5, wherein, Photosensitive agent B contains an oxime compound.

11. The resin composition according to any one of claims 1 to 5, further comprising an antioxidant.

12. The resin composition according to any one of claims 1 to 5, further comprising an aniline compound.

13. The resin composition according to any one of claims 1 to 5, further comprising a urea compound.

14. The resin composition according to any one of claims 1 to 5, used for forming an interlayer insulating film for a redistribution layer.

15. A cured product formed by curing the resin composition according to any one of claims 1 to 5.

16. A laminate comprising two or more layers made of the cured material of claim 15, wherein a metal layer is included between any of the layers made of the cured material.

17. A method for manufacturing a cured material, comprising: The film forming process involves applying the resin composition of any one of claims 1 to 4 onto a substrate to form a film.

18. The method for manufacturing a cured product according to claim 17, comprising: The exposure process involves selectively exposing the film. The developing process involves using a developing solution to develop the film to form a pattern.

19. The method for manufacturing a cured product according to claim 17, comprising: The heating process involves heating the membrane at a temperature of 50–450°C.

20. A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in claim 17.

21. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in claim 17.

22. A semiconductor device comprising the cured material of claim 15.

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