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

Abstract

Disclosed are a photosensitive resin composition, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device comprising the method for producing the cured product, and a semiconductor device comprising the cured product. The photosensitive resin composition contains: a resin which is a polyimide having a polymerizable group and a weight average molecular weight of 5,000 or more and less than 30,000; a polymerizable compound; and a photopolymerization initiator.

Description

TECHNICAL FIELD

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

[0002] Nowadays, in various fields, resin materials manufactured from resin compositions containing resins are being utilized.

[0003] For example, as the use of the above-described resin material, there is no particular limitation, and if a semiconductor device for mounting is exemplified, the use as a material for an insulating film, a sealing material, or a protective film can be cited. Also, it can be used as a base film, a cover film, or the like of a flexible substrate.

[0004] The resin composition can be applied by a publicly known coating method or the like, and thus it can be said that the adaptability in production is excellent, for example, the degree of freedom in design of the shape, size, application position, and the like of the resin composition to be applied at the time of application is high. From the viewpoint that the adaptability in production is excellent, the industrial application of the above-described resin composition is increasingly expected to expand.

[0005] For example, in Patent Literature 1, a negative photosensitive resin composition containing (A) a polyimide having a double bond in a side chain, (B) a crosslinking agent containing a (meth)acrylate compound having a fluorene skeleton, and (C) a polymerization initiator is described.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Application Laid-Open No. 2022-135427 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] In recent years, signal high-speeding of inter-chip wiring has become increasingly important, and miniaturization and layering of re-wiring connecting chips are being performed. Therefore, in the cured product of the photosensitive resin composition used in the use of forming a pattern targeting re-wiring formation, insulation, and the like, further improvement in planarity is also required.

[0011] Also, in order to achieve the above-described layering, improvement in the resistance to chemicals (chemical resistance) of the cured product to a developing solution or the like is also required.

[0012] The present invention aims to provide a photosensitive resin composition that yields a cured product with excellent flatness and chemical resistance, a cured product obtained by curing the above composition, a laminate containing the above 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.

[0013] means for solving technical problems

[0014] The following are examples of representative embodiments of the present invention.

[0015] <1> A photosensitive resin composition comprising:

[0016] The resin is a polyimide having polymerizable groups and a weight-average molecular weight of 5,000 or more and less than 30,000.

[0017] Polymer compounds; and

[0018] Photopolymerization initiator.

[0019] <2> A resin composition comprising:

[0020] The resin is selected from at least one of the groups consisting of polyimides and their precursors;

[0021] Polymer compounds; and

[0022] Photopolymerization initiator,

[0023] Of the three cured products with different thicknesses that underwent thermogravimetric analysis under the following testing conditions 1, at least one had a mass reduction rate of less than 5% by mass.

[0024] The shrinkage rate before and after curing is less than 15%.

[0025] Measurement conditions 1:

[0026] A cured product was obtained by heating a film of the above-mentioned photosensitive resin composition, formed on a silicon substrate with a thickness of 5 μm, 10 μm, or 20 μm, at 230°C for 3 hours. The mass reduction rate of the cured product was measured when the temperature was increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then increased from 260°C to 300°C at a rate of 10°C / min.

[0027] The aforementioned mass reduction rate is calculated using the following formula A.

[0028] Formula A: Mass reduction rate (%) = {1 - (mass of the membrane after heating at 300℃) / (mass of the membrane at 25℃)} × 100

[0029] <3> according to <2> The photosensitive resin composition, wherein,

[0030] Among the three cured products with different thicknesses that underwent thermogravimetric analysis under the following measurement conditions 2, at least one product had a mass reduction rate of less than 5% by mass.

[0031] Measurement condition 2:

[0032] A cured product was obtained by heating a film of the above-described resin composition, which is formed on a silicon substrate with a thickness of 5 μm, 10 μm, or 20 μm, at 170°C for 2 hours. The mass reduction rate of the cured product was measured when the temperature was increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then increased from 260°C to 300°C at a rate of 10°C / min.

[0033] The aforementioned mass reduction rate is calculated using the following formula A.

[0034] Formula A: Mass reduction rate (%) = {1 - (mass of the membrane after heating at 300℃) / (mass of the membrane at 25℃)} × 100

[0035] <4> according to <1> to <3> The photosensitive resin composition described in any one of the following statements, wherein,

[0036] The weight-average molecular weight of the above resin is 10,000 or more and less than 25,000.

[0037] <5> according to <1> to <4> The photosensitive resin composition described in any one of the following statements, wherein,

[0038] The above resin composition satisfies the following condition 1.

[0039] Condition 1:

[0040] A cured product was obtained by heating a film of the above-described resin composition, which is formed on a silicon substrate with a thickness of 15 μm, at 230°C for 3 hours. When the glass transition temperature of the cured product returned to 25°C was measured using a differential scanning calorimeter, the glass transition temperature was found to be 180–260°C.

[0041] <6> according to <1> to <5> The photosensitive resin composition described in any one of the following statements, wherein,

[0042] The melting point of the above polymeric compounds is below 25°C.

[0043] <7> according to <1> to <6> The photosensitive resin composition described in any one of the following statements, wherein,

[0044] The content of the above-mentioned polymeric compound is 1 to 40 parts by mass relative to 100 parts by mass of the above-mentioned resin composition.

[0045] <8> according to <1> to <7> The photosensitive resin composition described in any one of the following statements, wherein,

[0046] The glass transition temperature of the above resin is 180–260°C.

[0047] <9> according to <1> to <8> The photosensitive resin composition described in any one of the following statements, wherein,

[0048] The resin described above contains repeating units represented by the following formula (1-1).

[0049] [Chemical Formula 1]

[0050]

[0051] In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of these groups independently represents an organic group with a polymerizable group, where m represents an integer from 0 to 4 and n represents an integer greater than 1.

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

[0053] The above X 1 and Y 1 Each of the above is an organic group that independently contains an organic group having a structure formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-10).

[0054] [Chemical Formula 2]

[0055]

[0056] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0057] 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.

[0058] In equation (V-8), R X5 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0059] <11> according to <9> or <10> The photosensitive resin composition, wherein,

[0060] The above R 1 It represents the group represented by formula (R-1).

[0061] [Chemical Formula 3]

[0062]

[0063] In equation (R-1), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an aromatic group or a cyclic aliphatic group. 1 Indicates a polymerizable group, a1 indicates 0 or more and Z 1 Integers below the largest substitution base, a2 represents integers above 1, and * represents X in equation (1-1). 1 Or Y 1 The bonding sites.

[0064] <12> according to <1> to <11> The photosensitive resin composition described in any one of the following examples is used to form an insulating component.

[0065] <13> according to <1> to <12> The photosensitive resin composition described in any one of the following is used to form an interlayer insulating film for a rewiring layer.

[0066] <14> A solidified substance, which is... <1> to <13> It is formed by curing the photosensitive resin composition described in any one of the above.

[0067] <15> A laminate containing two or more layers of material. <14> The cured material forms a layer, wherein a metal layer is included between any of the layers formed by the cured material.

[0068] <16> A method for manufacturing a cured material, comprising: <1> to <13> The photosensitive resin composition described in any one of the above statements is suitable for a film forming process in which a film is formed on a substrate.

[0069] <17> according to <16> The method for manufacturing the solidified material includes:

[0070] The exposure process selectively exposes the aforementioned film; and

[0071] In the developing process, the above film is developed using a developing solution to form a pattern.

[0072] <18> according to <16> or <17> The method for manufacturing the cured material includes a heating step of heating the film at 50 to 450°C.

[0073] <19> A method for manufacturing a laminate, comprising: <16> to <18> The method for manufacturing the cured product as described in any one of the above.

[0074] <20> A method for manufacturing a semiconductor device, comprising: <16> to <18> The method for manufacturing the cured product as described in any one of the above.

[0075] <21> A semiconductor device comprising <14> The solidified product mentioned above.

[0076] Invention Effects

[0077] According to the present invention, a photosensitive resin composition that yields a cured product with excellent flatness and chemical resistance is provided, a cured product obtained by curing the above composition, a laminate containing the above 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. Attached Figure Description

[0078] Figure 1 This is a schematic cross-sectional view of a silicon wafer with a solidified material formed on it, where copper wiring has been formed. Detailed Implementation

[0079] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0080] In this specification, the numerical range represented by the symbol “~” refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0081] In this specification, the term "process" refers not only to independent processes, but also to processes that cannot be clearly distinguished from other processes as long as they can achieve the intended function of the process.

[0082] In the designation of groups (atomic groups) in this specification, the designations without substitution and without substitution include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0083] 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 for 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.

[0084] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either one.

[0085] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0086] 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 components other than the solvent relative to the total mass of the composition.

[0087] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, for example, an HLC-8220 GPC (manufactured by TOSOH CORPORATION) is used, 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 a column, from which the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined. Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. In cases where THF is unsuitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, the detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm.

[0088] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or 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." In addition, this setting of up and down directions is for the convenience of explaining this specification, and in practice, the "upper" direction in this specification may also be different from the vertically upward direction.

[0089] In this specification, unless otherwise specified, each component in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0090] Unless otherwise specified, the temperature in this instruction manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0091] In this specification, the preferred combination of methods is a more preferred method.

[0092] (Photosensitive resin composition)

[0093] The photosensitive resin composition (hereinafter also simply referred to as the "first resin composition") according to the first aspect of the present invention comprises: a resin, which is a polyimide having polymerizable groups and a weight-average molecular weight of 5,000 or more and less than 30,000; a polymerizable compound; and a photopolymerization initiator.

[0094] The photosensitive resin composition (hereinafter also simply referred to as the "second resin composition") according to the second aspect of the present invention contains: at least one resin selected from the group consisting of polyimide and its precursors; a polymerizable compound; and a photopolymerization initiator. Among three cured products with different thicknesses that were subjected to thermogravimetric analysis under the following measurement conditions 1, at least one of them has a mass reduction rate of 5% or less and a shrinkage rate of less than 15% before and after curing.

[0095] Measurement conditions 1:

[0096] A cured product was obtained by heating a film of the above-mentioned photosensitive resin composition, formed on a silicon substrate with a thickness of 5 μm, 10 μm, or 20 μm, at 230°C for 3 hours. The mass reduction rate of the cured product was measured when the temperature was increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then increased from 260°C to 300°C at a rate of 10°C / min.

[0097] The aforementioned mass reduction rate is calculated using the following formula A.

[0098] Formula A: Mass reduction rate (%) = {1 - (mass of the membrane after heating at 300℃) / (mass of the membrane at 25℃)} × 100

[0099] Hereinafter, the first resin composition and the second resin composition will also be simply referred to as "resin composition".

[0100] Hereinafter, the resin contained in the first resin composition having repeating units represented by formula (1-1) is also referred to as the "first specific resin".

[0101] Hereinafter, at least one resin selected from the group consisting of polyimide and its precursors contained in the second resin composition is also referred to as the "second specific resin".

[0102] Hereinafter, when simply referred to as "specific resin", it refers to both the first specific resin and the second specific resin.

[0103] 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.

[0104] 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 insulating components.

[0105] An insulating component is a component formed between parts for the purpose of insulating them from electrical conductivity, such as in wiring. The volume resistivity of the insulating component is preferably 1×10⁻⁶. 8 Ω·cm or more, more preferably 1×10 10 Ω·cm or higher, and more preferably 1×10 12 Ω·cm or higher.

[0106] In particular, using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer is also one of the preferred embodiments of the present invention.

[0107] Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative development.

[0108] In this invention, negative development refers to development in which non-exposed areas are removed by development during exposure and development, while positive development refers to development in which exposed areas are removed by development.

[0109] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and developing method described in the developing step can be used.

[0110] The resin composition according to the present invention can yield cured products with excellent flatness and chemical resistance.

[0111] The mechanism by which these effects are achieved is not yet clear, but the following is a hypothesis.

[0112] The photosensitive resin composition according to the first aspect of the present invention contains a polyimide having polymerizable groups and a weight-average molecular weight of 5,000 or more and less than 30,000.

[0113] It is believed that by containing such a low molecular weight polyimide, even when the composition is applied to a substrate with an uneven surface to form a film and then cured to form a cured product, the film can easily follow the unevenness of the composition and the flatness of the obtained cured product can be improved.

[0114] However, when using only polyimides with small molecular weights, chemical resistance sometimes deteriorates.

[0115] Therefore, in this invention, polymerizable groups are introduced into polyimide.

[0116] It is believed that by forming polymers between polyimides or between polyimides and polymeric compounds through the polymeric group, the chemical resistance of the obtained cured product is improved.

[0117] In the photosensitive resin composition according to the second aspect of the present invention, the mass reduction rate determined by a specific method is 5% by mass or less, and the shrinkage rate before and after curing is 15% by mass or less.

[0118] It is believed that by using such a photosensitive resin composition with low shrinkage before and after curing, even when the cured product is formed on a substrate with unevenness, the difference between the unevenness and the thick and thin portions of the coating film formed on the concave and convex portions is reduced, and a cured product with excellent flatness can be obtained.

[0119] Furthermore, it is believed that a small mass reduction rate indicates fewer low-molecular-weight components, and since the dissolution of the agent is also more difficult, it is thought that a cured product with excellent chemical resistance can be obtained.

[0120] Therefore, according to the present invention, both chemical resistance and flatness of the obtained cured material can be achieved.

[0121] Here, no resin composition corresponding to the resin composition of the present invention is described in Patent Document 1.

[0122] <Physical Properties of Cured Resin Compositions>

[0123] [Quality Reduction Rate]

[0124] Among the three cured products with different thicknesses when the first resin composition of the present invention was used to perform a thermogravimetric analysis under the following measurement conditions 1, the mass reduction rate of at least one cured product is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0125] Among the three cured products with different thicknesses when thermal mass measurements were performed using the second resin composition of the present invention under the following measurement conditions 1, at least one of them had a mass reduction rate of 5% or less by mass, preferably 4% or less by mass, and more preferably 3% or less by mass.

[0126] The mass reduction rate was determined under the following test conditions 1.

[0127] Measurement conditions 1:

[0128] A cured product was obtained by heating a film of the above-mentioned photosensitive resin composition, formed on a silicon substrate with a thickness of 5 μm, 10 μm, or 20 μm, at 230°C for 3 hours. The mass reduction rate of the cured product was measured when the temperature was increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then increased from 260°C to 300°C at a rate of 10°C / min.

[0129] The aforementioned mass reduction rate is calculated using the following formula A.

[0130] Formula A: Mass reduction rate (%) = {1 - (mass of the membrane after heating at 300℃) / (mass of the membrane at 25℃)} × 100

[0131] Here, there is no particular limitation on the method of applying the resin composition, as long as the distance from the substrate to the film surface is 5μm, 10μm, or 20μm, respectively, but spin coating can be used. Furthermore, if it is difficult to form a film with the aforementioned distance of 20μm in a single spin coating, multiple spin coatings can be performed. Even so, if it is difficult to form a film with the aforementioned distance of 20μm by spin coating, an appropriate application method can be selected from known methods such as dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, slot coating, and inkjet coating.

[0132] When the resin composition contains a solvent, drying is preferably performed after the above-described process. In this case, the distance from the substrate to the surface of the dried film is referred to as the thickness.

[0133] Drying is preferably carried out until the amount of solvent in the membrane is 0.5% by mass or less.

[0134] There are no particular limitations on the drying conditions; drying can be carried out by heating. Furthermore, if it is difficult to achieve sufficient drying by heating alone, pressure reduction can be applied.

[0135] It can be dried under atmospheric conditions. In cases where the resin composition contains components that are easily modified by oxygen, drying can also be carried out under conditions such as displacement by inactive gases like nitrogen or under vacuum.

[0136] There are no particular limitations on drying methods; heating plates and the like can be used. Furthermore, when pressure reduction or inactive gas replacement is required, ovens with pressure reduction functions or ovens with gas replacement functions can also be used.

[0137] In the case of heat-based drying, the heating temperature (drying temperature) can be, for example, 100°C. However, if drying at 100°C is difficult, the drying temperature can be appropriately varied between 70°C and 130°C (preferably 90°C to 120°C) depending on the type of solvent contained in the resin composition.

[0138] In the case of heat-based drying, the drying time (the time for which the heating temperature is supplied) can be, for example, 5 minutes. If it is difficult to dry within 5 minutes, the drying time can be appropriately changed to 30 seconds to 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the resin composition.

[0139] In the case of heat-based drying, the heating rate used to heat the drying film is not particularly limited, and can be set to, for example, 5°C / min. If drying is difficult to achieve within the above heating rate, the heating rate can be appropriately changed to between 1 and 12°C / min or 2 and 10°C / min, depending on the type of solvent contained in the resin composition.

[0140] A cured product is obtained by heating the film of the resin composition obtained by the above treatment at 230°C for 3 hours.

[0141] Heating is applied to the film of the obtained resin composition to minimize exposure. Furthermore, contact with solvents such as developing solutions is also minimized.

[0142] The above heating can be carried out in a nitrogen atmosphere using an oven.

[0143] The pressure during the heating process is set to 1 atmosphere (101,325 Pa).

[0144] The heating rate described above can be set to, for example, 10°C / minute.

[0145] The heating time (exposure time to 230°C) in the above heating process is set to 3 hours.

[0146] Specifically, the aforementioned mass reduction rate can be determined using the methods described in the embodiments described later.

[0147] The aforementioned mass reduction rate can be adjusted according to the structure and content of specific resins, polymeric compounds, etc. contained in the resin composition.

[0148] In the resin composition of the present invention, among the three cured products with different thicknesses when thermal mass measurement was performed under the following measurement conditions 2, at least one of them preferably has a mass reduction rate of 5% or less by mass, more preferably 4% or less by mass, and even more preferably 3% or less by mass.

[0149] Measurement condition 2:

[0150] A cured product was obtained by heating a film of the above-described resin composition, which is formed on a silicon substrate with a thickness of 5 μm, 10 μm, or 20 μm, at 170°C for 2 hours. The mass reduction rate of the cured product was measured when the temperature was increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then increased from 260°C to 300°C at a rate of 10°C / min.

[0151] The aforementioned mass reduction rate is calculated using the following formula A.

[0152] Formula A: Mass reduction rate (%) = {1 - (mass of the membrane after heating at 300℃) / (mass of the membrane at 25℃)} × 100

[0153] In the detailed description of the test method in test condition 2, the temperature used to obtain the cured product is changed from 230°C to 170°C. Otherwise, the detailed description of the test method in test condition 1 is the same, and the preferred method is also the same.

[0154] Shrinkage rate before and after curing

[0155] The shrinkage rate of the first resin composition of the present invention before and after curing is preferably less than 15%, more preferably less than 12%, and even more preferably less than 10%.

[0156] The shrinkage rate of the second resin composition of the present invention before and after curing is less than 15%, preferably less than 12%, and more preferably less than 10%.

[0157] Regarding the shrinkage rate before and after curing, the film was formed by applying the resin composition to a silicon wafer with a thickness of 15 μm. The shrinkage rate was calculated as the rate of change of the thickness of the cured product obtained by heating at 230°C for 3 hours after full-surface exposure, relative to the thickness of the cured product before exposure (15 μm).

[0158] Specifically, when the thickness of the cured material is set as film thickness B, it is calculated using the following formula.

[0159] Calculation formula: Shrinkage rate (%) = 100 - (film thickness B ÷ 15 × 100)

[0160] As a method for applying a resin composition to a silicon wafer, the application methods described in the above description of mass reduction rate, other than setting the thickness to 15 μm, can be listed.

[0161] Furthermore, if the resin composition contains a solvent, drying is preferably performed after the above-described process. In this case, the distance from the substrate to the surface of the dried film is 15 μm.

[0162] As a method for performing the above-mentioned drying, other drying methods described in the explanation of the mass reduction rate, besides setting the thickness to 15 μm, can be listed.

[0163] Full-area exposure was performed using a stepper (e.g., Nikon NSR 2005 i9C) at 500 mJ / cm². 2 The method involves i-ray exposure using specific exposure energy. However, if the photopolymerization initiator is not photosensitive when using the exposure wavelength and sensitivity described above, the exposure wavelength and sensitivity can be appropriately changed. Specifically, the exposure wavelength and sensitivity can be changed when the photopolymerization initiator is not photosensitive at a concentration of 50 mol% or more. Whether the photopolymerization initiator is photosensitive can be determined by changes in its structure.

[0164] A cured product is obtained by heating the film of the above-mentioned exposed resin composition at 230°C for 3 hours.

[0165] As a method for performing the above-mentioned heating, the heating method described in the above description of the mass reduction rate can be listed.

[0166] The shrinkage rate before and after curing can be adjusted according to the structure and content of specific resins, polymeric compounds, etc. contained in the resin composition.

[0167] The film thickness of the cured material was measured after the cured material was cooled to 25°C.

[0168] Glass transition temperature

[0169] The resin composition of the present invention preferably satisfies the following condition 1.

[0170] If the glass transition temperature measured under condition 1 below is above 180°C, the heat resistance is excellent, the thicker parts of the resin composition become less volatile and deformable, and thus the flatness is improved.

[0171] When the glass transition temperature, as measured under condition 1 below, is below 260°C, molecular mobility is enhanced, making polymerizable groups easier to polymerize and resulting in excellent chemical resistance. Furthermore, the compatibility of specific resins with other components, such as polymerizable compounds, is improved, thus suppressing the aggregation of generating components and resulting in excellent flatness.

[0172] The glass transition temperature in condition 1 below is preferably 200–260°C, more preferably 230–260°C.

[0173] Condition 1: A cured product was obtained by heating a film of the above-described resin composition, which is formed on a silicon substrate with a thickness of 15 μm, at 230°C for 3 hours. When the glass transition temperature of the cured product returned to 25°C was measured using a differential scanning calorimeter, the glass transition temperature was 180–260°C.

[0174] The cured product was obtained by heating at 230°C for 3 hours after the resin composition was applied to a silicon wafer to form a film.

[0175] As a method for applying a resin composition to a silicon wafer, the application method described in the above description of the mass reduction rate can be cited.

[0176] Furthermore, if the resin composition contains a solvent, it is preferable to perform drying after the above-described process.

[0177] As a method for performing the above-mentioned drying, the drying method described in the above description of the mass reduction rate can be listed.

[0178] A cured product is obtained by heating the film of the above-mentioned dried resin composition at 230°C for 3 hours.

[0179] As a method for performing the above-mentioned heating, the heating method described in the above description of the mass reduction rate can be listed.

[0180] The glass transition temperature of the cured product obtained in this way was determined.

[0181] Specifically, by changing the temperature conditions of the cured material in the following order (1) to (4), a differential scanning calorimetry (DSC) curve is prepared. The temperature at the intersection of the line drawn by extending the baseline of the low-temperature side of the DSC curve to the high-temperature side and the tangent line drawn at the point where the curve gradient changes the most in the stage-change part of the glass transition can be determined.

[0182] (1) Increase the temperature from 25℃ to 300℃ at a rate of 10℃ / minute.

[0183] (2) Cool from 300℃ to 25℃

[0184] (3) Increase the temperature from 25℃ to 500℃ at a rate of 10℃ / minute.

[0185] (4) Cool from 500℃ to 25℃

[0186] Furthermore, for details regarding the method for determining the glass transition temperature, please refer to the methods described in the examples described later.

[0187] The glass transition temperature can be adjusted according to the structure and content of specific resins, polymeric compounds, etc. contained in the resin composition.

[0188] Furthermore, the resin composition of the present invention preferably satisfies the following condition 2.

[0189] Regarding the cured product obtained by heating at 170°C for 3 hours, the glass transition temperature in condition 2 is preferably 200–260°C, more preferably 230–260°C.

[0190] Condition 2: The above resin composition was applied to a silicon substrate with a thickness of 15 μm, dried at 100°C for 5 minutes, and then heated at 170°C for 3 hours to obtain a cured product. When the glass transition temperature of the cured product was measured at 25°C using a differential scanning calorimeter, the glass transition temperature was found to be 180–260°C.

[0191] In the detailed description of the method for determining the glass transition temperature in condition 2 above, the heating temperature used to obtain the cured product is changed from 230°C to 170°C. Otherwise, the detailed description of the method for determining the glass transition temperature in condition 1 above is the same, and the preferred method is also the same.

[0192] The components contained in the resin composition of the present invention will be described in detail below.

[0193] <Specific Resin>

[0194] The second specific resin is at least one resin selected from the group consisting of polyimide and its precursors, preferably polyimide.

[0195] Polyimide precursors refer to resins that become polyimides by undergoing changes in molecular structure through external stimulation, preferably resins that become polyimides by undergoing changes in molecular structure through heat, and more preferably resins that become polyimides by forming a ring structure through a ring-closing reaction caused by heat.

[0196] The preferred polyimide is at least one resin selected from the group consisting of polyimides, polyamide-imides, and polyester-imides.

[0197] For example, the preferred polyimide is at least one resin selected from the group consisting of a polyimide having repeating units represented by formula (1-1) as described below, a polyimide (polyamide-imide) having repeating units represented by formula (1-3) as described below, and a polyimide (polyester-imide) having repeating units represented by formula (1-5) as described below.

[0198] The second specific resin is preferably one having polymerizable groups.

[0199] As a polymerizable group, it can be a cationic polymerizable group, preferably a free radical polymerizable group.

[0200] Examples of polymerizable groups include epoxy groups, oxetyl groups, alkoxymethyl groups, acyloxymethyl groups, hydroxymethyl groups, terminal isocyanate groups, and groups containing olefinic unsaturated bonds, with groups containing olefinic unsaturated bonds being preferred.

[0201] The group containing an olefinic unsaturated bond is preferably a free radical polymerizable group.

[0202] Furthermore, examples of groups containing olefinic unsaturated bonds include vinyl, vinyl ether, allyl, isoallyl, 2-methylallyl, (meth)acrylamido, and (meth)acryloyloxy groups. From the viewpoint of low polarity and reducing the dielectric constant of the obtained cured product, vinyl or vinyl ether groups are preferred. Here, the aforementioned vinyl group is preferably directly bonded to the aromatic ring structure.

[0203] In this invention, direct bonding of a structure A with other structures B means that structure A and structure B are bonded by single bonds without the use of connecting groups.

[0204] The first specific resin is a polyimide having polymerizable groups and a weight-average molecular weight of 5,000 or more and less than 30,000.

[0205] The first specific resin is defined as having polymerizable groups, a weight-average molecular weight of 5,000 or more and less than 30,000, and being a polyimide, otherwise being the same as the second specific resin, and the preferred method is also the same.

[0206] Glass transition temperature

[0207] The glass transition temperature (Tg) of a particular resin is preferably 180–260°C, more preferably 200–260°C, and even more preferably 230–260°C.

[0208] As long as the glass transition temperature is above 180°C, the heat resistance is excellent, and the thicker parts of the resin composition become less volatile and deformable, thus improving the flatness.

[0209] When the glass transition temperature is below 260°C, molecular mobility is enhanced, making polymerizable groups easier to polymerize and resulting in excellent chemical resistance. Furthermore, the compatibility of specific resins with other components such as polymerizable compounds is improved, thus suppressing the aggregation of generating components and resulting in excellent flatness.

[0210] The glass transition temperature of a specific resin can be determined by using the specific resin instead of the cured product in the method described in Condition 1 above.

[0211] The glass transition temperature mentioned above can be adjusted according to the structure of a specific resin (such as structures derived from anhydrides or diamines) and the ring closure rate.

[0212] When the resin composition contains two or more specific resins, it is preferable that the Tg of at least one specific resin is within the above range, but it is also one of the preferred embodiments of the present invention that the Tg of all specific resins is within the above range.

[0213] Furthermore, when the resin composition contains two or more specific resins, it is preferable that the weighted average value corresponding to the content ratio of these resins is within the above-mentioned range. For example, when the A1:A2 content ratio contains two specific resins with Tg values ​​of Tg1 and Tg2 respectively (A1+A2=1), the above-mentioned weighted average value is the value calculated by Tg1×A1+Tg2×A2.

[0214] The preferred resin is one that has a ring structure with 5 or more cyclic atoms on its side chain.

[0215] In this invention, the main chain of the resin refers to the longest bonded chain in the resin molecule. Furthermore, when the main chain contains ring structures, the atoms contained in the ring structures as ring-forming atoms are the atoms contained in the main chain.

[0216] In this invention, the side chain of the resin refers to the molecular chain bonded to the main chain, which may or may not have repeating units. That is, the molecular chain may or may not contain repeating structures. Furthermore, the molecular chain is preferably composed of 6 or more atoms, more preferably of 10 or more atoms, and even more preferably of 15 or more atoms. The upper limit of the number of atoms contained in the molecular chain is not particularly limited, for example, preferably 1,000 or less, more preferably 500 or less.

[0217] Here, the side chain in a particular resin is preferably bonded to a carbon atom contained in the main chain. When the side chain is represented by R, it is preferable that the side chain R is bonded to a carbon atom C of the main chain in the form of CR. That is, the bond between a side chain and the main chain is preferably only one.

[0218] The ring structure having 5 or more ring atoms is preferably a ring structure having 5 to 20 ring atoms, and more preferably a ring structure having 5 to 12 ring atoms.

[0219] As a ring structure with 5 or more ring atoms, it can be any of an aromatic ring or an aliphatic ring, preferably an aromatic ring or an aliphatic hydrocarbon ring, and more preferably an aromatic ring.

[0220] As an aromatic ring, it can be any of an aromatic hydrocarbon ring or a heteroaromatic ring, preferably an aromatic hydrocarbon ring or a heteroaromatic ring containing a nitrogen atom as a cyclizing atom.

[0221] As an aromatic hydrocarbon ring, it is preferably an aromatic hydrocarbon ring with 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring with 6 to 10 carbon atoms, and even more preferably a benzene ring.

[0222] Examples of heteroaromatic rings include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, imidazole rings, triazole rings, tetraazole rings, oxazole rings, pyridine rings, pyridazine rings, pyrazine rings, triazine rings, indole rings, indazole rings, benzimidazole rings, and purine rings.

[0223] Examples of aliphatic rings include aliphatic hydrocarbon rings with 5 to 20 carbon atoms, pyrrolidine rings, pyrrolidine rings, pyrazolidine rings, imidazoidine rings, tetrahydrofuran rings, tetrahydrothiophene rings, piperidine rings, piperazine rings, tetrahydropyran rings, dioxane rings, and morpholine rings.

[0224] Among these, the ring structure having 5 or more ring atoms is preferably a benzene ring, a cyclohexane ring, or an adamantane ring, with a benzene ring being the most preferred.

[0225] A ring structure with 5 or more cyclic atoms can replace hydrogen atoms that are bonded by single bonds without passing through cyclic atoms and linking groups. Examples of substituents include alkyl groups, aryl groups, halogen atoms, and polymerizable groups described later.

[0226] The content of ring structures with 5 or more cyclic atoms in a specific resin is preferably 0.01 to 5.0 mmol / g, more preferably 0.1 to 4.0 mmol / g, and even more preferably 0.5 to 2.5 mmol / g, relative to 1g of the specific resin.

[0227] The particular resin is preferably composed of the structure represented by the following formula (A-1).

[0228] [Chemical Formula 4]

[0229]

[0230] In equation (A-1), L A1 Cy represents a single bond or a linking group with an m+1 valence. Cy independently represents a cyclic structure with 5 or more cyclic atoms and may have substituents. m represents an integer greater than 1. * represents a bonding site with other structures.

[0231] In equation (A-1), LA1 Preferably, it is a linker group with a valence of m+1. L A1 The preferred method is the same as L in the following formula (R-1) 1 The preferred method is the same.

[0232] In formula (A-1), the preferred method for Cy is the same as the preferred method for the ring structure with 5 or more ring atoms mentioned above.

[0233] Furthermore, Cy is preferably directly bonded to the polymeric groups described later.

[0234] In formula (A-1), * indicates a bonding site with other structures, preferably a bonding site with atoms contained in the main chain of the resin, and more preferably a bonding site with carbon atoms contained in the main chain. The aforementioned carbon atom is preferably a tertiary carbon atom or a quaternary carbon atom.

[0235] The structure represented by equation (A-1) is preferably not included in the main chain.

[0236] Furthermore, the structure represented by formula (A-1) is also one of the preferred embodiments of the present invention as the structure represented by formula (R-1) described later.

[0237] The content of the structure represented by formula (A-1) in a specific resin is preferably 0.01 to 5.0 mmol / g, more preferably 0.1 to 4.0 mmol / g, and even more preferably 0.5 to 2.5 mmol / g, relative to 1g of the specific resin.

[0238] [The repeating unit represented by equation (1-1)]

[0239] The specific resin is preferably a repeating unit represented by the following formula (1-1).

[0240] [Chemical Formula 5]

[0241]

[0242] In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of these groups independently represents an organic group with a polymerizable group, where m represents an integer from 0 to 4 and n represents an integer greater than 1.

[0243] -R 1 -

[0244] R 1 Each of these organic groups is an independent organic group having a polymerizable group. The preferred manner of the polymerizable group is the same as that described in the second specific resin above.

[0245] Here, R 1 Preferably, it contains a ring structure with 5 or more cyclic atoms.

[0246] Furthermore, R 1 The preferred structure is the one represented by formula (R-1).

[0247] [Chemical Formula 6]

[0248]

[0249] In equation (R-1), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an aromatic group or a cyclic aliphatic group. 1 Indicates a polymerizable group, a1 indicates 0 or more and Z 1 Integers below the largest substitution base, a2 represents integers above 1, and * represents X in equation (1-1). 1 Or Y 1 The bonding sites.

[0250] In equation (R-1), L 1 Preferably, it is a group represented by the following formula (L-1).

[0251] [Chemical Formula 7]

[0252]

[0253] In equation (L-1), L x This represents a linking group with a valence of a2+1, where a2 represents an integer greater than or equal to 1, and * represents the linkage with X in equation (1-1). 1 Or Y 1 The bonding site, # indicates the bond with Z in equation (R-1). 1 The bonding sites.

[0254] L x Preferably, it is an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and especially preferably a methylene group.

[0255] The preferred method for a2 in equation (L-1) is the same as the preferred method for a2 in equation (R-1).

[0256] Z in equation (R-1) 1 These represent aromatic groups or cyclic aliphatic groups. The preferred configurations of these groups are the same as those for ring structures with 5 or more cyclic atoms in the first specific resin described above.

[0257] A in equation (R-1) 1The polymeric group is indicated by the same preferred manner as the polymeric group in the first specific resin and the second specific resin described above.

[0258] Wherein, the preferred option is A in formula (R-1) contained in formula (1-1). 1 At least one of them is vinyl, (meth)acryloyloxy, vinyl ether, allyl, epoxy or a group containing these, more preferably vinyl or vinyl ether.

[0259] In formula (R-1), a1 is preferably an integer from 0 to 2, more preferably 0 or 1. Furthermore, a1 being 1 or 2 is also one of the preferred embodiments of the present invention.

[0260] In formula (R-1), a2 represents an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0261] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0262] -X 1 -

[0263] In equation (1-1), X 1 Preferably, it represents an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-10).

[0264] Chemical resistance and flatness are improved by using organic groups containing structures formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-10).

[0265] Here, by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of formulas (V-1) to (V-5), effects such as suppressing the generation of developing residue, reducing the dielectric constant of the cured product, and decreasing the coefficient of thermal expansion can also be obtained.

[0266] Here, by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of formulas (V-6) to (V-10), it is also possible to obtain effects such as the pattern being less likely to become conical due to the increased transmittance of ultraviolet light and a wider tolerance for exposure.

[0267] [Chemical Formula 8]

[0268]

[0269] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0270] 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.

[0271] In equation (V-8), R X5 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0272] In equation (V-2), R X1 Each of the components is preferably an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0273] In equation (V-3), R X2 and R X3 Each atom is preferably a hydrogen atom.

[0274] 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 -CR2-, more preferably -O- or -C(R)2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, alkyl or aryl, and even more preferably a hydrogen atom.

[0275] In equation (V-8), R X5 Each of the components is preferably an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0276] In X 1 In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), X 1 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (1-1). 1 In the bonding sites of the four carbonyl groups, n1 represents an integer from 0 to 5, and is preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1replace.

[0277] [Chemical Formula 9]

[0278]

[0279] In X 1 In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), X 1 Preferably, the group represented by formula (V-2-1) or formula (V-2-2) is preferred. From the viewpoint of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. In this specification, the bond that crosses the edge of the ring structure refers to any one of the hydrogen atoms that replaces the ring structure. In the following formula, L X1 The asterisk (*) represents a single bond or -O-, and the asterisk (*) represents the X in equation (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X1 The definition and preferred method are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydroxyl groups and hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0280] [Chemical Formula 10]

[0281]

[0282] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), X 1 Preferably, the group represented by formula (V-3-1) or formula (V-3-2) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-2) is preferred. In the following formulas, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X2 and R X3 The definition and preferred method are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydroxyl groups and hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0283] [Chemical Formula 11]

[0284]

[0285] In X 1In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), X 1 Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups are defined by n1, which is an integer from 0 to 5. Furthermore, the hydrogen atoms in the structure described below can be further replaced by known substituents such as hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 Substitution. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted.

[0286] [Chemical Formula 12]

[0287]

[0288] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-5), X 1 Preferably, it is a group represented by the following formula (V-5-1). In the following formula, * represents X in formula (1-1). 1 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 hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0289] [Chemical Formula 13]

[0290]

[0291] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-6), X 1 Preferably, it is a group represented by the following formula (V-6-1). In the following formula, * represents X in formula (1-1). 1 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 hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0292] [Chemical Formula 14]

[0293]

[0294] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-7), X 1 Preferably, it is a group represented by the following formula (V-7-1). In the following formula, * represents X in formula (1-1). 1 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 hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0295] [Chemical Formula 15]

[0296]

[0297] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-8), X 1 Preferably, it is a group represented by the following formula (V-8-1). In the following formula, * represents X in formula (1-1). 1 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 hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0298] [Chemical Formula 16]

[0299]

[0300] In X 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-9), X 1 Preferably, it is a group represented by the following formula (V-9-1). In the following formula, * represents X in formula (1-1). 1 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 hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0301] [Chemical Formula 17]

[0302]

[0303] In X1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-10), X 1 Preferably, it is a group represented by the following formula (V-10-1). In the following formula, * represents X in formula (1-1). 1 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 hydroxyl groups or hydrocarbon groups. And, when m in the above formula (1-1) is an integer from 1 to 4, it is preferable that m hydrogen atoms are replaced by R in formula (1-1). 1 replace.

[0304] [Chemical Formula 18]

[0305]

[0306] In addition, X 1 R can be derived from equation (4) in the following statement. 132 The group represented is formed by removing m hydrogen atoms.

[0307] And, X 1 Preferably, the structure does not contain an imide structure.

[0308] In this invention, the imide structure is represented by -C(=O)N(-*)C(=O)-. * indicates a bonding site with other structures.

[0309] And, X 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0310] 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; * indicates the bonding site with a carbon atom, respectively. R N Preferably, it is a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.

[0311] 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, and * indicates a bonding site with a carbon atom. R N The preferred method is as described above.

[0312] In this invention, the amide bond is *-NR. N The key represented by -C(=O)-*, R N Represents a hydrogen atom or a monovalent organic group; * indicates the bonding site with a carbon atom, respectively. RN The preferred method is as described above.

[0313] Additionally, X 1 Preferably, the structure does not contain ester bonds.

[0314] In this invention, the ester bond is represented by the bond represented by *-OC(=O)-*.

[0315] Among these, X 1 Preferably, it does not contain imide structures, urethane bonds, urea bonds, and amide bonds; more preferably, it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0316] -Y 1 -

[0317] In equation (1-1), Y 1 Preferably, it contains a group that has a structure formed by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10).

[0318] Chemical resistance and flatness are improved by using organic groups containing structures formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-10).

[0319] Here, by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of formulas (V-1) to (V-5), effects such as suppressing the generation of developing residue, reducing the dielectric constant of the cured product, and decreasing the coefficient of thermal expansion can also be obtained.

[0320] Here, by using an organic group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any of formulas (V-6) to (V-10), it is also possible to obtain effects such as the pattern being less likely to become conical due to the increased transmittance of ultraviolet light and a wider tolerance for exposure.

[0321] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y 1 Preferably, it is a group obtained by removing n hydrogen atoms from the group represented by the following formula (V-1-2). In the following formula, * represents Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms, where n1 represents an integer from 1 to 5. In the following structure, the n hydrogen atoms are bounded by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0322] [Chemical Formula 19]

[0323]

[0324] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y 1 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-, * indicates a Y in equation (1-1) 1 The bonding sites of the two nitrogen atoms. Furthermore, R X1 The preferred method is as described above. In the following structure, the n hydrogen atoms are multiplied by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydroxyl groups and hydrocarbon groups.

[0325] [Chemical Formula 20]

[0326]

[0327] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), Y 1 Preferably, the group represented by formula (V-3-3) or formula (V-3-4) is preferred. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-3) is preferred. In the following formulas, * represents Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, R X2 and R X3 The preferred method is as described above. In the following structure, the n hydrogen atoms are multiplied by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydroxyl groups and hydrocarbon groups.

[0328] [Chemical Formula 21]

[0329]

[0330] In Y 1 In the case of a group comprising a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), Y 1Preferably, it is a group represented by the following formula (V-4-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites 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. In the following structure, the n hydrogen atoms are multiplied by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0331] [Chemical Formula 22]

[0332]

[0333] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-5), Y 1 Preferably, it is a group represented by the following formula (V-5-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. The n hydrogen atoms in the following structure are bounded by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0334] [Chemical Formula 23]

[0335]

[0336] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-6), Y 1 Preferably, it is a group represented by the following formula (V-6-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. The n hydrogen atoms in the following structure are bounded by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0337] [Chemical Formula 24]

[0338]

[0339] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-7), Y1 Preferably, it is a group represented by the following formula (V-7-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. The n hydrogen atoms in the following structure are bounded by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0340] [Chemical Formula 25]

[0341]

[0342] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-8), Y 1 Preferably, it is a group represented by the following formula (V-8-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. The n hydrogen atoms in the following structure are bounded by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0343] [Chemical Formula 26]

[0344]

[0345] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-9), Y 1 Preferably, it is a group represented by the following formula (V-9-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. The n hydrogen atoms in the following structure are bounded by R in formula (1-1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0346] [Chemical Formula 27]

[0347]

[0348] In Y 1 In the case of a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by formula (V-10), Y 1Preferably, it is a group represented by the following formula (V-10-2). In the following formula, * represents the group corresponding to Y in formula (1-1). 1 The bonding sites of the two nitrogen atoms. The n hydrogen atoms in the following structure, represented by R in formula (1v1). 1 Substitution. The meaning of n is the same as that of n in formula (1-1). Furthermore, the hydrogen atoms in the following structures can be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0349] [Chemical Formula 28]

[0350]

[0351] In addition, Y 1 R can be derived from equation (4) in the following statement. 131 The group represented is formed by removing n hydrogen atoms.

[0352] Furthermore, Y 1 Preferably, the structure does not contain an imide structure.

[0353] Furthermore, Y 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0354] In addition, Y 1 Preferably, the structure does not contain ester bonds.

[0355] Among these, Y 1 Preferably, it does not contain imide structures, urethane bonds, urea bonds, and amide bonds; more preferably, it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0356] Among these, X in equation (1-1) is preferred. 1 and Y 1 These are organic groups containing structures formed by removing two or more hydrogen atoms from the structures represented by any of the formulas (V-1) to (V-10) described above. Preferred embodiments of these groups are as described above.

[0357] In addition, X 1 It can be R in equation (4) as described later. 132 The same group, Y 1 It can be R in equation (4) as described later. 131 Same group.

[0358] For example, X can be listed 1 An organic group containing an organic group formed by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10), and Y 1 For R in equation (4) mentioned later 131The same group in the way, X 1 For R in equation (4) mentioned later 132 Same group and Y 1 This includes organic groups containing structures formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-10) above.

[0359] In formula (1-1), m is preferably an integer from 0 to 2, more preferably 0 or 1. Furthermore, m being 0 is also one of the preferred embodiments of the present invention.

[0360] In formula (1-1), n ​​is preferably 1 or 2, and more preferably 2.

[0361] In addition to the repeating unit represented by formula (1-1), the first specific resin may also contain repeating units represented by formula (1-2).

[0362] The second specific resin is also preferably a repeating unit represented by formula (1-2).

[0363] [Chemical Formula 29]

[0364]

[0365] In equation (1-2), A 1 and A 2 Each independently represents an oxygen atom or -NR. z -, X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each group independently represents a polymerizable group, R 113 and R 114 R represents either a hydrogen atom or a monovalent organic group independently. z It represents a hydrogen atom or a monovalent organic group, where m represents an integer from 0 to 4 and n represents an integer greater than 1.

[0366] X in equation (1-2) 1 Y 1 R 1 The preferred methods for n and m are the same as those for X in equation (1-1) above. 1 Y 1 R 1 The optimal selection methods for n and m are the same.

[0367] A in equation (1-2) 1 A 2 R 113 and R 114 The preferred method is the same as A in equation (2) described later. 1 A2 R 113 and R 114 The preferred method is the same.

[0368] In addition to the repeating unit represented by formula (1-1), the first specific resin may also contain repeating units represented by formula (1-3).

[0369] The second specific resin is also preferably a repeating unit represented by formula (1-3).

[0370] [Chemical Formula 30]

[0371]

[0372] In equation (1-3), X 2 Y represents a 3+m valence linking group. 2 R represents a linking group with a 2+n valence. 1 Each is an organic group that has a polymerizable group, m represents an integer from 0 to 4, and n represents an integer greater than 1.

[0373] In equation (1-3), X 2 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, these are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0374] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these.

[0375] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0376] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, and all hydrogen atoms may be replaced by halogen atoms, but it is preferable that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0377] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0378] And, X 2 Preferably, it is a tricarboxylic acid compound derived from at least one carboxyl group that can be halogenated. As the halogenation mentioned above, chlorination is preferred.

[0379] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0380] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated.

[0381] Examples of tricarboxylic acid compounds that can be halogenated and used as precursors for polyamide imides include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0382] These tricarboxylic acid compounds can be used in one or more forms.

[0383] X 2 Preferably, the structure does not contain an imide structure.

[0384] And, X 2 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0385] Additionally, X 2 Preferably, the structure does not contain ester bonds.

[0386] Among these, X 1 Preferably, it does not contain imide structures, urethane bonds, urea bonds, and amide bonds; more preferably, it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0387] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a tricarboxylic acid compound formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound containing an aromatic group with 6 to 20 carbon atoms or a tricarboxylic acid compound formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0388] Furthermore, specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked by single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or phenylene oxide.

[0389] These compounds can be compounds in which two carboxyl groups are anhydrinated (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride acyl chloride).

[0390] In equation (1-3), Y 2 R 1 The meanings of , n and m are respectively the same as those of Y in the above formula (1-1). 1 R 1 The meanings of , n, and m are the same, and the optimization methods are also the same.

[0391] In the case where a particular resin contains repeating units represented by formula (1-3), it is preferable to contain repeating units represented by the following formula (1-3-2).

[0392] [Chemical Formula 31]

[0393]

[0394] In equation (1-3-2), X 2 Each of the following independently represents a 3+m valence linking group, Y 2 Each independently represents a linking group with a 2+n valence, R 1 Each of these groups is an organic group that has a polymerizable group, m independently represents an integer from 0 to 4, n independently represents an integer greater than 1, and L... 3 This indicates a divalent linker.

[0395] In equation (1-3-2), X 2 Y 2 R 1 The preferred method for , m, n is the same as X in the above formula (1-3).2 Y 2 R 1 The optimal selection methods for m and n are the same.

[0396] In equation (1-3-2), L 3 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, these are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0397] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these.

[0398] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0399] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, and all hydrogen atoms may be replaced by halogen atoms, but it is preferable that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0400] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0401] In addition to the repeating unit represented by formula (1-1), the first specific resin may also contain repeating units represented by formula (1-4).

[0402] The second specific resin is also preferably a repeating unit represented by formula (1-4).

[0403] [Chemical Formula 32]

[0404]

[0405] In equation (1-4), X 2 Y represents a 3+m valence linking group. 2 R represents a linking group with a 2+n valence. 1 Each is an organic group that independently possesses a polymerizable group, where m represents an integer from 0 to 4, n represents an integer greater than or equal to 1, and A 2 Represents oxygen atom or -NR z -, R z R represents a hydrogen atom or a monovalent organic group. 113 It represents a hydrogen atom or an organic group with a valence of 1.

[0406] X in equation (1-4) 2 Y 2 R 1 The preferred methods for n and m are the same as those for X in equation (1-3) above. 2 Y 2 R 1 The optimal selection methods for n and m are the same.

[0407] A in equation (1-4) 2 and R 113 The preferred method is the same as A in equation (2) described later. 2 and R 113 The preferred method is the same.

[0408] In the case where a particular resin contains repeating units represented by formula (1-4), it is preferable to contain repeating units represented by the following formula (1-4-2).

[0409] [Chemical Formula 33]

[0410]

[0411] In equation (1-4-2), X 2 Each of the following independently represents a 3+m valence linking group, Y 2 Each independently represents a linking group with a 2+n valence, R 1 Each of these groups is an organic group that has a polymerizable group, m independently represents an integer from 0 to 4, and n independently represents an integer greater than 1. 2 Each independently represents an oxygen atom or -NR. z -, R z R represents either a hydrogen atom or a monovalent organic group independently. 113 Each can independently represent a hydrogen atom or a monovalent organic group, L 3 This indicates a divalent linker.

[0412] In equation (1-4-2), X 2 Y 2 R 1 m, n, A 2 and R 113 The preferred method is the same as X in the above formula (1-4). 2 Y 2 R 1 m, n, A 2 and R 113 The preferred method is the same.

[0413] In equation (1-4-2), L 3 The preferred method is the same as L in the above formula (1-3-2). 3 The preferred method is the same.

[0414] In addition to the repeating unit represented by formula (1-1), the first specific resin may also contain repeating units represented by formula (1-5).

[0415] The second specific resin is also preferably a repeating unit represented by formula (1-5).

[0416] [Chemical Formula 34]

[0417]

[0418] In equation (1-5), X 2 Y represents a 3+m valence linking group. 2 R represents a linking group with a 2+n valence. 1 Each is an organic group that has a polymerizable group, m represents an integer from 0 to 4, and n represents an integer greater than 1.

[0419] In equation (1-5), X 2 Y 2 R 1 The preferred methods for m and n are respectively related to X in equation (1-3). 2 Y 2 R 1 The preferred methods for m and n are the same.

[0420] In the case where a particular resin contains repeating units represented by formula (1-5), it is preferable to contain repeating units represented by the following formula (1-5-2).

[0421] [Chemical Formula 35]

[0422]

[0423] In equation (1-5-2), X 2 Each of the following independently represents a 3+m valence linking group, Y 2Each independently represents a linking group with a 2+n valence, R 1 Each of these groups is an organic group that has a polymerizable group, m independently represents an integer from 0 to 4, n independently represents an integer greater than 1, and L... 3 This indicates a divalent linker.

[0424] In equation (1-5-2), X 2 Y 2 R 1 m, n and L 3 The preferred method is the same as X in the above formula (1-3-2). 2 Y 2 R 1 m, n and L 3 The preferred method is the same.

[0425] In addition to the repeating unit represented by formula (1-1), the first specific resin may also contain repeating units represented by formula (1-6).

[0426] The second specific resin is also preferably a repeating unit represented by formula (1-6).

[0427] [Chemical Formula 36]

[0428]

[0429] In equation (1-6), X 2 Y represents a 3+m valence linking group. 2 R represents a linking group with a 2+n valence. 1 Each is an organic group that independently possesses a polymerizable group, where m represents an integer from 0 to 4, n represents an integer greater than or equal to 1, and A 2 Represents oxygen atom or -NR z -, R z R represents a hydrogen atom or a monovalent organic group. 113 It represents a hydrogen atom or an organic group with a valence of 1.

[0430] X in equation (1-6) 2 Y 2 R 1 The preferred methods for n and m are the same as those for X in equation (1-5) above. 2 Y 2 R 1 The optimal selection methods for n and m are the same.

[0431] A in equation (1-6) 2 and R 113 The preferred method is the same as A in equation (2) described later. 2 and R 113 The preferred method is the same.

[0432] In the case where a particular resin contains repeating units represented by formula (1-6), it is preferable to contain repeating units represented by the following formula (1-6-2).

[0433] [Chemical Formula 37]

[0434]

[0435] In equation (1-6-2), X 2 Each of the following independently represents a 3+m valence linking group, Y 2 Each independently represents a linking group with a 2+n valence, R 1 Each of these groups is an organic group that has a polymerizable group, m independently represents an integer from 0 to 4, and n independently represents an integer greater than 1. 2 Each independently represents an oxygen atom or -NR. z -, R z R represents either a hydrogen atom or a monovalent organic group independently. 113 Each can independently represent a hydrogen atom or a monovalent organic group, L 3 This indicates a divalent linker.

[0436] In equation (1-6-2), X 2 Y 2 R 1 m, n, A 2 and R 113 The preferred method is the same as X in the above formula (1-6). 2 Y 2 R 1 m, n, A 2 and R 113 The preferred method is the same.

[0437] In equation (1-6-2), L 3 The preferred method is the same as L in the above formula (1-3-2). 3 The preferred method is the same.

[0438] A particular resin may contain repeating units represented by formula (2).

[0439] The repeating unit corresponding to the repeating unit represented by equation (1-2) is set to not correspond to the repeating unit represented by equation (2).

[0440] [Chemical Formula 38]

[0441]

[0442] In equation (2), A 1 and A 2Each independently represents an oxygen atom or -NR. z -, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 R represents either a hydrogen atom or a monovalent organic group independently. z It represents a hydrogen atom or an organic group with a valence of 1.

[0443] A in equation (2) 1 and A 2 Each independently represents an oxygen atom or -NR. z - Preferably, it contains oxygen atoms.

[0444] R z It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0445] R in equation (2) 111 This represents a divalent organic group. As R 111 Examples of functional groups described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421 may be cited. These descriptions are incorporated into this specification.

[0446] Furthermore, R 111 Preferably, it contains a group that has a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10), and does not have a group that is similar to the above R. 1 The group at the bonding site. Except for those that do not have a bond with R. 1 Apart from the bonding site, this group is preferably associated with containing Y from the above formulas (1-2). 1 The preferred mode for the group of the structure obtained by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-10) is the same.

[0447] Regarding R 115 Specifically, examples include the tetracarboxylic acid residues remaining after the anhydride group is removed from tetracarboxylic dianhydrides. As for R... 115 The corresponding structure, the first specific resin or the second specific resin may contain only one tetracarboxylic dianhydride residue, or it may contain two or more tetracarboxylic dianhydride residues.

[0448] As tetracarboxylic acid dianhydrides, compounds described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421 can be listed. These descriptions are incorporated into this specification.

[0449] Furthermore, R 115Preferably, it contains a group that has a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10), and does not have a group that is similar to the above R. 1 The group at the bonding site. Except for those that do not have a bond with R. 1 Apart from the bonding site, this group is preferably associated with X from the above formula (1-2). 1 The preferred mode is the same for the groups that form structures by removing two or more hydrogen atoms from the structures represented by any of the formulas (V-1) to (V-10) contained herein.

[0450] In equation (2), R 111 and R 115 At least one of them can also have an OH group. More specifically, as R 111 The residues of bisaminophenol derivatives can be listed.

[0451] R in equation (2) 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. As R 113 and R 114 Examples of functional groups described in paragraphs 0058 to 0063 of Japanese Patent Application Publication No. 2023-003421 may be cited. These descriptions are incorporated into this specification.

[0452] The first specific resin and the second specific resin may contain repeating units represented by formula (4).

[0453] The repeating unit corresponding to the repeating unit represented by equation (1-1) is set to not correspond to the repeating unit represented by equation (4).

[0454] [Chemical Formula 39]

[0455]

[0456] In equation (4), R 131 R represents a divalent organic group. 132 This indicates a tetravalent organic group.

[0457] R 131 This represents a divalent organic group. Examples of divalent organic groups include R in formula (2). 111 For the same functional groups, the preferred range is also the same.

[0458] As R 131 Examples of diamines include the diamine residues remaining after the amino group of the diamine is removed. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, R in formula (2) of a polyimide precursor can be cited. 111 Examples.

[0459] From the perspective of more effectively suppressing warping during calcination, R 131 Preferably, it is a diamine residue having at least two alkylene glycol units on the main chain. More preferably, it is a diamine residue containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in a molecule. Even more preferably, it is a diamine residue that does not contain an aromatic ring.

[0460] Examples of diamines that contain a total of two or more ethylene glycol chains or propylene glycol chains in a single molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but are not limited to these.

[0461] R 132 This represents a tetravalent organic group. Examples of tetravalent organic groups include R in formula (2). 115 For the same functional groups, the preferred range is also the same.

[0462] For example, as R 115 The four bonds of the exemplified tetravalent organic group are bonded to the four -C(=O)- portions in formula (4) to form a fused ring.

[0463] R 132 Examples include the tetracarboxylic acid residues remaining after the anhydride group is removed from a tetracarboxylic dianhydride. As a specific example, R in formula (2) of the polyimide precursor can be cited. 115 Examples. From the viewpoint of the strength of organic membranes, R 132 Preferably, it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0464] It is also preferred to be in R 131 and R 132 At least one of them has an OH group. More specifically, as R 131 Examples of preferred embodiments include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, as well as (DA-1) to (DA-18) above. 132 Examples of better practices can be listed as (DAA-1) to (DAA-5).

[0465] The first specific resin and the second specific resin may contain repeating units represented by formula (PAI-2).

[0466] [Chemical Formula 40]

[0467]

[0468] In formula (PAI-2), R 117 R represents a trivalent organic group. 111 A represents a divalent organic group. 2 Represents oxygen atom or -NH-, Z 1 Represents oxygen atom or -NH-, R 113 It represents a hydrogen atom or an organic group with a valence of 1.

[0469] In formula (PAI-2), R 117 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, these are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0470] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these.

[0471] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0472] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, and all hydrogen atoms may be replaced by halogen atoms, but it is preferable that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0473] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0474] Furthermore, R 117 Preferably, it is a tricarboxylic acid compound derived from at least one carboxyl group that can be halogenated. As the halogenation mentioned above, chlorination is preferred.

[0475] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0476] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated.

[0477] Examples of tricarboxylic acid compounds include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0478] These tricarboxylic acid compounds can be used in one or more forms.

[0479] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a tricarboxylic acid compound formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound containing an aromatic group with 6 to 20 carbon atoms or a tricarboxylic acid compound formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0480] Furthermore, specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked by single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or phenylene oxide.

[0481] These compounds can be compounds in which two carboxyl groups are anhydrinated (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride acyl chloride).

[0482] In formula (PAI-2), R 111 A 2 R 113 The meanings are respectively the same as R in the above formula (2). 111 A 2 R 113 The meanings are the same, and the preferred methods are also the same.

[0483] A particular resin may contain repeating units represented by formula (PAI-1).

[0484] [Chemical Formula 41]

[0485]

[0486] In formula (PAI-1), R 116 R represents a divalent organic group. 111 This indicates a divalent organic group.

[0487] In the formula (PAI-1), R is exemplified 116 It is a group consisting of straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, it is a group consisting of straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a group consisting of aromatic groups with 6 to 20 carbon atoms or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0488] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, alkyl halide, arylene, or linking groups formed by bonding two or more of these.

[0489] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0490] The alkyl halide described above is preferably an alkyl halide with 1 to 20 carbon atoms, more preferably an alkyl halide with 1 to 10 carbon atoms, and even more preferably an alkyl halide with 1 to 4 carbon atoms. Furthermore, examples of halogen atoms in the alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The alkyl halide may have hydrogen atoms, and all hydrogen atoms may be replaced by halogen atoms, but it is preferable that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene.

[0491] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0492] Furthermore, R 116Preferably, it is derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0493] In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound.

[0494] In dicarboxylic acid dihalide compounds, the carboxyl group only needs to be halogenated, for example, preferably chlorinated. That is, dicarboxylic acid dihalide compounds are preferably dicarboxylic acid dichloride compounds.

[0495] Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that can be halogenated include straight-chain or branched aliphatic, cyclic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0496] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used in one or more forms.

[0497] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferably a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms through single bonds or linking groups.

[0498] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, and hexafluoro... Sebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyldiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0499] As a specific example of a dicarboxylic acid dihalide compound, a compound with a structure formed by halogenating two carboxyl groups from the above-mentioned dicarboxylic acid compound examples can be listed.

[0500] In formula (PAI-1), R 111 The meaning of R is the same as that in equation (2) above. 111 The meanings are the same, and the preferred methods are also the same.

[0501] When the specific resin is polyimide, the content of the repeating unit represented by formula (1-1) relative to the total mass of the specific resin is preferably 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0502] When the specific resin is polyimide, the total content of the repeating units represented by formula (1-1), formula (1-3), and formula (1-5) relative to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0503] When the specific resin is polyimide, the total content of the repeating units represented by formula (1-1), formula (1-3-2), and formula (1-5-2) relative to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0504] Furthermore, a particular resin may contain repeating units of two or more structures contained in the particular resin. In this case, it is preferable that the total amount is within the above-mentioned range.

[0505] When the specific resin is polyimide, the total content of the repeating units represented by formula (1-1), formula (1-3), formula (1-5), and formula (4) relative to the total mass of the specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited, and may also be 100% by mass.

[0506] Furthermore, when the specific resin is polyimide, the total content of the repeating units represented by formula (1-1), formula (1-3-2), formula (1-5-2), and formula (4) relative to the total mass of the specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0507] Furthermore, in the case where a particular resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) with different structures. In this case, it is preferable that the total amount is within the above-mentioned range.

[0508] When the second specific resin is a polyimide precursor, the content of the repeating unit represented by formula (1-2) relative to the total mass of the second specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0509] When the second specific resin is a polyimide precursor, the total content of the repeating units represented by formula (1-2), formula (1-4), and formula (1-6) relative to the total mass of the second specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0510] When the second specific resin is a polyimide precursor, the total content of the repeating units represented by formula (1-2), formula (1-4-2), and formula (1-6-2) relative to the total mass of the second specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0511] Furthermore, a particular resin may contain repeating units of two or more structures contained in the particular resin. In this case, it is preferable that the total amount is within the above-mentioned range.

[0512] When the second specific resin is a polyimide precursor, the total content of the repeating units represented by formulas (1-2) and (2) relative to the total mass of the second specific resin is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. The upper limit of the above content is not particularly limited and may also be 100% by mass.

[0513] Furthermore, if the first specific resin or the second specific resin contains a repeating unit represented by formula (2), it may contain two or more repeating units represented by formula (2) with different structures. In this case, it is preferable that the total amount is within the above-mentioned range.

[0514] When the second specific resin is polyimide, the weight-average molecular weight (Mw) is preferably 3,000 to 100,000.

[0515] The lower limit of Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.

[0516] The upper limit of Mw is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 25,000 or less.

[0517] By setting the weight-average molecular weight to 3,000 or higher, the folding resistance of the cured film can be improved. For organic films with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 5,000 or higher is particularly preferred.

[0518] The weight-average molecular weight of the first specific resin is greater than 5,000 and less than 30,000.

[0519] The lower limit of Mw is preferably 8,000 or more, and more preferably 10,000 or more.

[0520] The upper limit of Mw is preferably 28,000 or less, more preferably 25,000 or less.

[0521] The number average molecular weight (Mn) of the polyimide is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.

[0522] The molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular limitation on the upper limit of the molecular weight dispersion of the polyimide; for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0523] When the resin composition contains multiple polyimides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple polyimides are used as a single resin are each within the above-mentioned ranges.

[0524] When the specific resin is a polyimide precursor, the weight-average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0525] The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular limitation on the upper limit of the molecular weight dispersion of the polyimide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less.

[0526] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0527] When the resin composition contains multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. Furthermore, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple polyimide precursors are used as a single resin are each within the above-mentioned ranges.

[0528] When the resin is polyimide, from the viewpoint of the obtained organic film's strength and insulation properties, the imidization rate (also known as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the above imidization rate; it is acceptable as long as it is 100% or less.

[0529] Furthermore, when the specific resin is polyimide, the content of the imide structure in the specific resin is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, but can be set to 0.5 mmol / g or more, for example.

[0530] When the specific resin is a polyimide precursor, from the viewpoint of the obtained organic film's strength, insulation, etc., the imidization rate (also known as "ring-closing rate") of the polyimide precursor is preferably less than 70%, more preferably less than 50%, further preferably less than 20%, and especially preferably less than 10%. The lower limit of the above imidization rate is not particularly limited, as long as it is 0% or more.

[0531] For example, the imidization rate can be determined by the following method.

[0532] The infrared absorption spectrum of a specific resin was measured, and the absorption peak at 1377 cm⁻¹, which is derived from the imide structure, was determined. -1 The peak intensity P1 near the target was determined. Next, after heat-treating the specific resin at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity at 1377 cm⁻¹ was calculated. -1 The nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of a specific resin can be determined according to the following formula.

[0533] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0534] [Manufacturing method of specific resins]

[0535] For example, certain resins can be obtained by methods such as: reacting tetracarboxylic dianhydride with diamine at low temperature; reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid, and then esterifying it using a condensing agent or an alkylating agent; obtaining a diester by reacting tetracarboxylic dianhydride with an alcohol and then reacting it in the presence of diamine and a condensing agent; and obtaining a diester by reacting tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine. Of the above manufacturing methods, a more preferred method is obtaining a diester by reacting tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine.

[0536] Examples of condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0537] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0538] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0539] Furthermore, when a polyimide is desired as a specific resin, it can be synthesized using the following methods: a method for completely imidizing the resin obtained by the above method using a known imidization reaction; or a method for stopping the imidization reaction midway and introducing a partial imide structure; or a method for introducing a partial imide structure by mixing the fully imidized polymer with the polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0540] 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.

[0541] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0542] In a specific resin manufacturing method, it is preferable to add an alkaline compound during the reaction. The alkaline compound can be one type or two or more types.

[0543] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0544] -End- Capping Agent-

[0545] In the manufacturing method of a specific resin, to further improve storage stability, it is preferable to cap the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin terminus of the specific resin. When capping the carboxylic anhydride and anhydride derivative remaining at the resin terminus, end-capping agents include monools, phenols, thiols, thiophenols, and monoamines. Considering reactivity and film stability, monools, phenols, and monoamines are more preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds as monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. Examples of amino acids include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. More than two of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0546] Furthermore, when sealing the amino group at the end of the resin, compounds having functional groups capable of reacting with the amino group can be used for sealing. Preferred sealants for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of preferred carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentanoyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0547] Furthermore, based on the reaction of amino acids in compounds containing amino and hydroxyl groups, such as p-aminophenol, at the resin terminal, it is also possible to react the aforementioned hydroxyl groups with compounds that react with hydroxyl groups, such as 4-(chloromethyl)styrene. Through this reaction, polymerizable groups can be introduced at the terminal.

[0548] -Solid precipitation-

[0549] The manufacturing method of a specific resin may include a solid precipitation step. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain the specific resin. To improve the purification degree, the specific resin may be repeatedly subjected to operations such as re-dissolving, re-precipitating, and drying. In addition, a step of removing ionic impurities using an ion exchange resin may also be included.

[0550] [Specific example]

[0551] Specific examples of a particular resin may include polyimides (PI-1) to (PI-11), (PA-1), (PE-1), and polyimide precursors (SP-1) to (SP-3) in the examples described below, but the present invention is not limited thereto.

[0552] 〔content〕

[0553] The content of a specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, even more preferably 50% by mass or more, and most preferably 60% by mass or more, relative to the total solids content of the resin composition. Furthermore, the content of the 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 even more preferably 95% by mass or less, relative to the total solids content of the resin composition.

[0554] The resin composition of the present invention may contain only one specific resin or may contain two or more resins. When containing two or more resins, it is preferable that the total amount is within the above-mentioned range.

[0555] The resin composition of the present invention preferably contains at least two resins.

[0556] Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, and may contain two or more specific resins, preferably containing two or more specific resins.

[0557] When the resin composition of the present invention contains two or more specific resins, for example, it is preferably a polyimide precursor and contains two or more polyimide precursors with different structures derived from dianhydrides.

[0558] <Other Resins>

[0559] 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").

[0560] As other resins, to distinguish them from specific resins, examples include resins belonging to the categories of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamide-imide precursors, polyamide-imides, aromatic polyethers, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

[0561] As other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamide-imide precursors, and polyamide-imides, examples include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above descriptions are incorporated herein by reference.

[0562] There are no particular limitations on aromatic polyethers, but polyphenylene ether is preferred.

[0563] Polyphenylene ether is preferably composed of repeating units represented by the following formula (PE).

[0564] [Chemical Formula 42]

[0565]

[0566] In formula (PE), R E1 This represents a hydrogen atom or a substituent. Examples of substituents include halogen atoms, alkyl groups that may have substituents, alkoxy groups that may have substituents, amino groups, nitro groups, carboxyl groups, etc.

[0567] Furthermore, polyphenylene ether is preferably a compound having polymerizable groups.

[0568] The polymerizable groups described above are preferably epoxy groups, oxazolyl groups, oxazolyl groups, hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups, terminal isocyanate groups, or groups having olefinic unsaturated bonds, and more preferably groups having olefinic unsaturated bonds.

[0569] Examples of groups having an olefinic unsaturated bond include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (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.

[0570] When polyphenylene ether is a compound having polymerizable groups, the position of the polymerizable groups is not particularly limited. For example, a structure in which polymerizable groups are introduced at the end of the main chain is preferred.

[0571] Polyphenylene ether may contain other repeating units. The content of these other repeating units relative to the total mass of the polyphenylene ether is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0572] The number average molecular weight of polyphenylene ether is not particularly limited, but is preferably 500 to 50,000.

[0573] The lower limit of the number-average molecular weight is preferably 800 or more, more preferably 1000 or more, and even more preferably 1500 or more.

[0574] The upper limit of the number-average molecular weight is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less.

[0575] Specific examples of polyphenylene ether (PPE) include, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), copolymers of 2,6-dimethylphenol with other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.), polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and polyphenylene ethers with linear or branched structures obtained by heating poly(2,6-dimethyl-1,4-phenylene ether) in toluene solvent in the presence of an organic peroxide to cause a redistribution reaction with phenolic compounds such as bisphenols or triphenols, but are not limited to these examples.

[0576] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solids 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.

[0577] The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0578] As a preferred embodiment of the resin composition of the present invention, it is also possible to set the content of other resins to be low. In the above embodiment, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0579] Furthermore, when the resin composition of the present invention contains other resins, the content of the specific resin relative to the total content of the specific resin and other resins is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and even more preferably 55 to 70% by mass.

[0580] 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 other resins, it is preferable that the total amount is within the above-mentioned range.

[0581] <Polymerizing compounds>

[0582] The resin composition of the present invention comprises a polymerizable compound.

[0583] The melting point of the polymerizable compound is preferably below 25°C.

[0584] By setting the melting point below 25°C, the coating film flows easily during drying and heating, which improves the flatness of the cured product.

[0585] In particular, from the viewpoint of reducing the dielectric constant of the cured product, the preferred polymerizable compound is one containing a ClogP value of 3.0 or higher, and more preferably a compound containing a ClogP value of 3.0 or higher and having an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms.

[0586] In this specification, the ClogP value of a compound depends on the following definition.

[0587] The octanol-water partition coefficient (logP value) can generally be determined by the flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). Furthermore, the octanol-water partition coefficient (logP value) can also be estimated using computational chemistry or empirical methods instead of actual measurement. Known calculation methods include Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), and Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)). In this invention, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used.

[0588] The ClogP value refers to the commonly used logarithm logP, which is used to calculate the partition coefficient P between 1-octanol and water. Regarding the method or software used in calculating the ClogP value, well-known methods can be used; unless otherwise stated, in this invention, the ClogP program of PCModels, a system assembled with Daylight Chemical Information Systems, is used.

[0589] The ClogP value is preferably 4.0 or higher, and more preferably 6.0 or higher.

[0590] Furthermore, the upper limit of the above ClogP value is not particularly limited, but is preferably below 15.0.

[0591] The aromatic ring structure described above can be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring, and more preferably containing a benzene ring. Furthermore, from the viewpoint of reducing the dielectric constant of the cured product, a fused ring such as a fluorene ring is preferred.

[0592] The aliphatic ring structure having 6 or more carbon atoms is preferably an aliphatic ring structure having 6 to 30 carbon atoms, and more preferably an aliphatic ring structure having 6 to 20 carbon atoms.

[0593] Aliphatic ring structures with 6 or more carbon atoms can be listed as monocyclic rings such as cyclohexane, bicyclic pentane, and tricyclic rings [5.2.1.0]. 2，6 Heterocyclic rings such as decane rings are preferred.

[0594] Polymerizable compounds with a ClogP value of 3.0 or higher (especially compounds with a ClogP value of 3.0 or higher and having an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms) are preferably compounds containing groups having olefinic unsaturated bonds, more preferably compounds containing two or more groups having olefinic unsaturated bonds. Furthermore, compounds containing two groups having olefinic unsaturated bonds are also preferred.

[0595] Furthermore, polymerizable compounds with a ClogP value of 3.0 or higher (especially compounds with a ClogP value of 3.0 or higher and having an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms) are preferably compounds corresponding to the free radical crosslinking agents described later.

[0596] Specific examples of polymeric compounds with a ClogP value of 3.0 or higher include the following compounds, but are not limited to them.

[0597] [Chemical Formula 43]

[0598]

[0599] [Chemical Formula 44]

[0600]

[0601] [Chemical Formula 45]

[0602]

[0603] As polymerizable compounds, free radical crosslinking agents or other crosslinking agents can be listed.

[0604] [Free radical cross-linking agent]

[0605] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0606] Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, these groups contain olefinically unsaturated bonds. Examples of such olefinically unsaturated groups include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0607] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl groups are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0608] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may also have three or more olefinic unsaturated bonds.

[0609] 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.

[0610] From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention is preferably a compound having two olefinic unsaturated bonds and a compound having three or more of the above-mentioned olefinic unsaturated bonds.

[0611] 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.

[0612] 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, addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Additionally, addition reactions of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides having deactivating substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as another example, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can also be used. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0613] 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 compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0614] Other preferred free radical crosslinking agents besides those mentioned above include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0615] Preferred free radical crosslinking agents 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.) and 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.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol or propylene glycol residues. Oligomer types can also be used.

[0616] Commercially available free radical crosslinking agents include, for example, tetrafunctional acrylates SR-494 with four ethoxy groups, difunctional methacrylates SR-209, 231, and 239 with four ethoxy groups (manufactured by Sartomer Company, Inc.), hexafunctional acrylates DPCA-60 with six pentenoxy groups, trifunctional acrylates TPA-330 with three isobutyleneoxy groups (manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). (manufactured by Kyoisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOFCORPORATION.), etc.

[0617] As a free radical crosslinking agent, urethane acrylates described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and urethane compounds having an ethylene oxide backbone described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418, are also preferred. Compounds having an amino or thioether structure within the molecule, as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238, can also be used as a free radical crosslinking agent.

[0618] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent having acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is 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, wherein the aliphatic polyhydroxy compound is a pentaerythritol or dipentaerythritol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

[0619] 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 was determined according to the description in JIS K 0070:1992.

[0620] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylate or acrylate.

[0621] 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, 1,6-hexanediol diacrylate, etc. 1,6-Hexanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct dimethacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct dimethacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified dimethacrylate, isocyanuric acid EO-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be used in combination as needed.

[0622] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of approximately 200 for the polyethylene glycol chain.

[0623] 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. Preferably, monofunctional free radical crosslinking agents include n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl (meth)acrylamide, glycidyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. Furthermore, to suppress volatilization before exposure, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred as monofunctional free radical crosslinking agents.

[0624] 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.

[0625] 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, and even more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0626] The free radical crosslinking agent can be used alone or in combination with two or more. When using two or more, it is preferable that their total amount is within the range mentioned above.

[0627] [Other crosslinking agents]

[0628] The resin composition of the present invention is also preferably composed of other crosslinking agents that are different from the free radical crosslinking agents described above.

[0629] 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 photosensitization by the aforementioned photoacid generators or photoalkali generators. They are also preferably 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 acids or bases.

[0630] 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.

[0631] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0632] The content of the polymerizable compound 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, and even more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0633] Furthermore, the content of the polymeric compound relative to 100 parts by weight of the resin composition is preferably 1 to 40 parts by weight, more preferably 3 to 30% by weight, and even more preferably 5 to 20% by weight.

[0634] The polymerizable compound can be used alone or in combination with two or more compounds. When using two or more compounds, it is preferable that their total amount is within the range described above.

[0635] [Photopolymerization initiator]

[0636] The resin composition of the present invention contains a photopolymerization initiator.

[0637] 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 sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, it can also be an active agent that reacts with a photoexcited sensitizer to generate active free radicals.

[0638] The photoradical polymerization initiator preferably contains at least one initiator having a wavelength of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be determined using known methods. For example, it is preferably determined using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0639] As photoradical polymerization initiators, any known compound 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, azide compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these compounds, 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.

[0640] 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.

[0641] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, as these are incorporated herein by reference.

[0642] 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.

[0643] 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.

[0644] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may also be used. This content is incorporated herein by reference.

[0645] Oxime compounds are more preferably used as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds have a wide exposure latitude (exposure margin) and also act as photocuring accelerators, making them particularly preferred.

[0646] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... The compounds described in Technology (1995, pp. 202-232), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0647] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In resin compositions, the use of oxime compounds as photoradical polymerization initiators is particularly preferred. Oxime compounds used as photoradical polymerization initiators have an intramolecular linking group >C=NOC(=O)-.

[0648] [Chemical Formula 46]

[0649]

[0650] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS 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). Furthermore, oxime compounds with the following structures can also be used.

[0651] [Chemical Formula 47]

[0652]

[0653] As photoradical polymerization initiators, for example, oxime compounds with fluorene rings, oxime compounds with at least one benzene ring forming a naphthalene ring skeleton, and oxime compounds with fluorine atoms, as described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189, can also be used.

[0654] Furthermore, it is also possible to use oxime compounds with nitro groups, oxime compounds with benzofuran skeletons, and oxime compounds with hydroxyl substituents bonded to a carbazole skeleton as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359. These contents are incorporated in this specification.

[0655] As a photopolymerization initiator, Ar aromatic cyclic groups with electron-withdrawing groups introduced onto the aromatic ring can also be used. OX1 Oxime compounds (hereinafter also referred to as oxime compounds OX). As the above aromatic cyclic group Ar... OX1Examples of electron-withdrawing groups include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano, with acyl and nitro being preferred. Acyl is more preferred due to its ease of forming a film with excellent lightfastness, and benzoyl is even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthioalkyl, arylthioalkyl, acyl, or amino, with alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthioalkyl, or amino being even more preferred, and alkoxy, alkylthioalkyl, or amino being even more preferred.

[0656] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0657] [Chemical Formula 48]

[0658]

[0659] In the formula, R X1 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphinyl, carbamoyl, or aminosulfonyl.

[0660] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0661] R X3 ~R X14 Each can be used to represent a hydrogen atom or a substituent independently.

[0662] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0663] In the above formula, R is preferred. X12 It is an electron-withdrawing group and R X10 R X11 R X13 R X14 It is a hydrogen atom.

[0664] As a specific example of the oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 is cited, which is incorporated in this specification.

[0665] Examples of particularly preferred oxime compounds include oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and oxime compounds with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

[0666] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0667] Furthermore, the photoradical polymerization initiator is a trihalomethane triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, it is at least one compound selected from the group consisting of trihalomethane triazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. More preferably, it is a metallocene compound or an oxime compound.

[0668] As a photoradical polymerization initiator, compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 and paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, as these are incorporated herein by reference.

[0669] As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such initiators, good sensitivity can be obtained because one molecule of the initiator generates two or more free radicals. Furthermore, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents and the like is improved, making it difficult for the resin composition to precipitate over time, thereby improving its long-term stability. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. The following are included in this specification: oxime ester photoinitiators as described in International Publication No. 2016 / 034963 (G), Cmpd1-7, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators as described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342 (A), and oxime ester photoinitiators as described in Japanese Patent Publication No. 6469669.

[0670] 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, their total amount is preferably within the above-mentioned range.

[0671] In addition, since photopolymerization initiators sometimes also function as thermal polymerization initiators, crosslinking using photopolymerization initiators is sometimes further carried out by heating in ovens, heating plates, etc.

[0672] [Sensitizer]

[0673] The resin composition may contain a sensitizer. The sensitizer absorbs specific active light and becomes electronically excited. The electronically excited sensitizer comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases.

[0674] As usable sensitizers, compounds of the following series can be used: benzophenone series, milchone series, coumarin series, pyrazole azo series, aniline azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, anthocyanin series, phenothiazine series, pyrrolopyrazole methylene azo series, guttan series, phthalocyanine series, benzopyran series, indigo series, etc.

[0675] Examples of sensitizers include 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-dimethylaminocinnamylindanone. Benzylindanone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamino Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0676] Furthermore, other sensitizing pigments can be used.

[0677] 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.

[0678] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used in combination.

[0679] [Chain transfer agent]

[0680] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferably used.

[0681] 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.

[0682] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solids content of the resin composition. 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 content is within the above range.

[0683] Furthermore, a photoacid generator can be used as a photopolymerization initiator. Preferably, a photoacid generator that generates free radicals is preferred.

[0684] Specifically, the preferred compound is one that absorbs light to decompose and generate free radicals, and extracts hydrogen from the solvent or the acid-generating agent itself to generate an acid.

[0685] Examples of photoacid-generating agents include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfones, and onium salts, with onium salts being preferred.

[0686] Examples of onium salts include diazonium salts, phosphine salts, sulfonium salts, and iodine salts.

[0687] Furthermore, onium salts are salts of cations and anions with onium structures, and these cations and anions may or may not be bonded by covalent bonds.

[0688] That is, the onium salt can be an intramolecular salt having a cationic and anionic portion within the same molecular structure, or it can be an intermolecular salt formed by ionic bonding of cationic and anionic molecules that are different molecules, but it is preferably an intermolecular salt. Furthermore, in the composition of the present invention, the above-mentioned cationic portion or cationic molecule can be bonded to or dissociated from the above-mentioned anionic portion or anionic molecule by ionic bonds.

[0689] [Sulfur]

[0690] In this invention, sulfonium salt refers to a salt of sulfonium cation and anion.

[0691] -sulfonium cation-

[0692] As a sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.

[0693] Furthermore, the preferred cation as a sulfonium cation is the cation represented by the following formula (103).

[0694] [Chemical Formula 49]

[0695]

[0696] In equation (103), R 8 ~R 10 Each hydrocarbon group can be represented independently.

[0697] R 8 ~R 10 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0698] R 8 ~R 10 It may also have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups with 3 to 10 carbon atoms or alkoxy groups with 1 to 10 carbon atoms.

[0699] R 8 ~R 10The groups can be the same or different groups; from the point of view of synthetic suitability, the same groups are preferred.

[0700] -Anion-

[0701] There are no specific restrictions on the anion; the choice should be based on the acid produced. However, B(C6F5)4 can be cited as an example. - BF4 - Boron-based anions, (Rf) n PF 6-n - PF3(C2F5) 3- PF6 - Phosphine anions, SbF6 - Antimony anions, other carboxylic acid anions, sulfonic acid anions, etc.

[0702] Iodized salt

[0703] In this invention, iodine salt refers to a salt of iodine cation and anion. Examples of anions include those identical to those in the above-described matte salts, and the preferred embodiments are also the same.

[0704] -iodocation-

[0705] As an iodine cation, a diaryliodocation is preferred.

[0706] Furthermore, the iodine cation is preferably the cation represented by the following formula (104).

[0707] [Chemical Formula 50]

[0708]

[0709] In equation (104), R 11 and R 12 Each hydrocarbon group can be represented independently.

[0710] R 11 and R 12 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0711] R 11 and R 12It may also have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups with 3 to 10 carbon atoms or alkoxy groups with 1 to 10 carbon atoms.

[0712] R 11 and R 12 The groups can be the same or different groups; from the point of view of synthetic suitability, the same groups are preferred.

[0713] [Scale salt]

[0714] In this invention, a sulfite salt refers to a salt of a sulfite cation and anion. Examples of anions include those identical to the anions in the sulfite salts described above, and the preferred embodiments are also the same.

[0715] -Lonium cation-

[0716] As a phosphonium cation, a quaternary phosphonium cation is preferred, and examples include tetraalkylphosphonium cations and triarylmonylphosphonium cations.

[0717] Furthermore, the preferred cation is the one represented by the following formula (105).

[0718] [Chemical Formula 51]

[0719]

[0720] In equation (105), R 13 ~R 16 Each can be used to represent a hydrogen atom or a hydrocarbon group independently.

[0721] R 13 ~R 16 Each is preferably alkyl or aryl, more preferably alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, even more preferably aryl with 6 to 12 carbon atoms, and even more preferably phenyl.

[0722] R 13 ~R 16 It may also have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, etc. Among these, it is preferable to have alkyl or alkoxy groups as substituents, more preferably to have branched alkyl or alkoxy groups, and even more preferably to have branched alkyl groups with 3 to 10 carbon atoms or alkoxy groups with 1 to 10 carbon atoms.

[0723] R 13 ~R16 The groups can be the same or different groups; from the point of view of synthetic suitability, the same groups are preferred.

[0724] The content of photoacid generator relative to the total solids content of the resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.

[0725] A single photoacid-generating agent can be used alone, or multiple agents can be used in combination. In the case of multiple combinations, it is preferable that the total amount of these agents is within the range described above.

[0726] Furthermore, in order to impart photosensitivity to the desired light source, it is preferable to use it in combination with a sensitizer.

[0727] Furthermore, the resin composition of the present invention containing two or more polymerization initiators is also one of the preferred embodiments of the present invention.

[0728] Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0729] By including a photopolymerization initiator and a thermal polymerization initiator (described later), it has properties such as the ability to perform exposure-based pattern formation, ease of free radical polymerization during curing based on the heating process (described later), and improved chemical resistance.

[0730] As for 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.

[0731] By including photoradical polymerization initiators and photoacid-producing agents, it has properties such as improved resolution.

[0732] As for the ratio of photopolymerization initiator and photoacid generator, the content of photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of photopolymerization initiator and photoacid generator.

[0733] [Thermal polymerization initiator]

[0734] 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 and 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.

[0735] As thermal free radical polymerization initiators, specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the contents of which are incorporated in this specification, can be cited.

[0736] When the resin composition contains a thermal polymerization 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, 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 thermal polymerization initiators. When containing two or more thermal polymerization initiators, the total amount is preferably within the above range.

[0737] <Alkali-generating agents>

[0738] 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.

[0739] In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains an alkali-generating agent. By containing a thermally alkali-generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, thereby resulting in good mechanical properties or chemical resistance of the cured product, and its performance as an interlayer insulating film for rewiring layers included in semiconductor packages becomes excellent.

[0740] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from the base-generating agent include, for example, secondary and tertiary amines.

[0741] There are no particular limitations on the alkali-generating agent; any known alkali-generating agent may be used. Examples of known alkali-generating agents include, for instance, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imine salts, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimide compounds.

[0742] Specific examples of nonionic base generating agents include compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0743] The following compounds can be cited as base-generating agents, but are not limited to these.

[0744] [Chemical Formula 52]

[0745]

[0746] [Chemical Formula 53]

[0747]

[0748] 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.

[0749] Specific preferred compounds for generating ionic bases include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0750] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[0751] [Chemical Formula 54]

[0752]

[0753] The following compounds can be cited as specific examples of imine salts, but are not limited to these.

[0754] [Chemical Formula 55]

[0755]

[0756] Furthermore, from the viewpoint of storage stability and the generation of alkali through deprotection during curing, an amine with an amino group protected by a tert-butoxycarbonyl group is preferred as an alkali generating agent.

[0757] Examples of amine compounds protected by the 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]benzylethanolamine. Compounds containing alcohols, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinol, 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-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxobis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxotetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxoundecane, or amino acids and their derivatives, wherein the amino group is protected by a tert-butoxycarbonyl group, but not limited to these.

[0758] 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.

[0759] One or more alkali-generating agents can be used. When using two or more, it is preferable that the total amount is within the above range.

[0760] Solvent

[0761] The resin composition of the present invention preferably contains a solvent.

[0762] 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.

[0763] 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, methyl 3-ethoxypropionate, etc.). Ethyl propionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred examples.

[0764] Examples of preferred ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0765] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0766] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred examples.

[0767] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0768] Preferred 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.

[0769] Examples of preferred urea compounds include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0770] 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.

[0771] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0772] In this invention, the solvent is preferably selected from one of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, L-glucosamine, dihydroL-glucosamine, or a mixed solvent consisting of two or more of these solvents. Particularly preferred methods include the use of dimethyl sulfoxide and γ-butyrolactone, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone and ethyl lactate. Further addition of approximately 1 to 10% by weight of toluene relative to the total mass of the solvent in these solvents is also a preferred method of the invention.

[0773] In particular, from the viewpoint of the storage stability of the resin composition, including γ-valerol as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerol 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. The above content can be determined by taking into account the solubility of the specific resin or other components contained in the resin composition.

[0774] Furthermore, when using dimethyl sulfoxide and γ-valerolactone together, the total mass relative to 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.

[0775] From the viewpoint of coatability, the solvent content is preferably set to an amount where the total solids concentration of the resin composition of the present invention reaches 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. Regarding the solvent content, it 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.

[0776] <Metal Adhesion Improver>

[0777] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion improver. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0778] [Silane coupling agent]

[0779] 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 silane coupling agent is also preferably a compound as follows: In the following formula, Me represents methyl and Et represents ethyl. Furthermore, the following R can be a structure derived from a capping agent with a capping isocyanate group. As a capping agent, it can be selected based on 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.).

[0780] [Chemical Formula 56]

[0781]

[0782] [Chemical Formula 57]

[0783]

[0784] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimeth ... 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-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0785] Furthermore, as a silane coupling agent, compounds of oligomer type having multiple alkoxysilyl groups can also be used.

[0786] Examples of this type of oligomer include compounds containing repeating units represented by the formula (S-1) below.

[0787] [Chemical Formula 58]

[0788]

[0789] 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.

[0790] R S1The 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.

[0791] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[0792] n represents an integer from 0 to 2, preferably 1.

[0793] Here, the repeating units represented by multiple formulas (S-1) contained in oligomer-type compounds may have the same structure.

[0794] Here, in the oligomer-type compound, among the multiple repeating units represented by formula (S-1), it is preferable that at least one has n of 1 or 2, more preferably that at least two have n of 1 or 2, and even more preferably that at least two have n of 1.

[0795] As for this type of oligomer compound, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0796] [Aluminum-based adhesive additives]

[0797] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0798] 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.

[0799] The content of the metal adhesion improver 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 improver may be only one type or may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0800] <Migration Inhibitors>

[0801] The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0802] There are no particular limitations on the migration inhibitors, and examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and thioalkyl groups, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0803] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0804] Other migration inhibitors include rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0805] The following compounds can be cited as specific examples of migration inhibitors.

[0806] [Chemical Formula 59]

[0807]

[0808] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor relative to the total solids 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.

[0809] There may be only one migration inhibitor or two or more. If there are two or more migration inhibitors, it is preferable that their total number is within the range mentioned above.

[0810] <Light absorber>

[0811] The resin composition of the present invention is also preferably a compound (light absorber) that reduces the absorbance of its exposure wavelength due to exposure.

[0812] 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.

[0813] 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.

[0814] <Polymerization Inhibitor>

[0815] 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.

[0816] Specific compounds that can be cited as polymerization inhibitors include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is incorporated herein by reference.

[0817] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0818] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the range mentioned above.

[0819] <Other Additives>

[0820] The resin composition of the present invention may contain various additives as needed within the scope of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, 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. Regarding these components, for example, reference can be made to paragraphs 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, their total content is preferably set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0821] [Inorganic particles]

[0822] 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.

[0823] 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.

[0824] 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.).

[0825] In cases where the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0826] [Organotitanium compounds]

[0827] By incorporating organic titanium compounds into the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0828] As usable organotitanium compounds, examples include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0829] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0830] I) Titanium chelate compounds: From the viewpoint of good storage stability of the resin composition and obtaining a good cured pattern, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples are bis(triethanolamine)diisopropoxide titanium, bis(n-butanol)bis(2,4-pentanedione) titanium, bis(2,4-pentanedione)diisopropoxide titanium, bis(tetramethylheptanedione)diisopropoxide titanium, bis(ethyl acetoacetate)diisopropoxide titanium, etc.

[0831] 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, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0832] III) Dioctenotin 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.

[0833] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzenesulfonate) isopropoxy titanium, etc.

[0834] V) Titanium oxide compounds: such as bis(pentanedione) titanium oxide, bis(tetramethylheptanedione) titanium oxide, phthalocyanine titanium oxide, etc.

[0835] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0836] VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonyl titanate, etc.

[0837] From the viewpoint of better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dicarboxylated titanium compounds is preferred as the organotitanium compound. In particular, bis(ethyl acetoacetate)diisopropoxide 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.

[0838] Furthermore, as an organotitanium compound or a substitute for an organotitanium compound, it is also preferable to include a compound represented by the following formula (T-1).

[0839] [Chemical Formula 60]

[0840]

[0841] In equation (T-1), M represents titanium, zirconium, or hafnium; l1 is an integer from 0 to 2; l2 is 0 or 1; l1 + l2 × 2 is an integer from 0 to 2; m is an integer from 0 to 4; n is an integer from 0 to 2; l1 + l2 + m + n × 2 = 4; R 11 R is independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted phenoxy. 12 For substituted or unsubstituted hydrocarbon groups, R 2 Each is an independent group comprising the structure represented by the following formula (T-2), R 3 Each is an independent group comprising the structure represented by the following formula (T-2), X A Each can be an oxygen atom or a sulfur atom, independently.

[0842] [Chemical Formula 61]

[0843]

[0844] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= are represented independently, with * indicating the bonding site with other structures and # indicating the bonding site with metal atoms, respectively.

[0845] In formula (T-1), from the viewpoint of the storage stability of the composition, M is preferably titanium.

[0846] In formula (T-1), the method in which l1 and l2 are 0 is also one of the preferred methods of the present invention.

[0847] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0848] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0849] In this case, in equation (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2 or 4.

[0850] In equation (T-1), considering the stability of a specific metal complex, R 11 Preferably, it is a substituted or unsubstituted cyclopentadiene ligand.

[0851] Furthermore, R 11The cyclopentadienyl, alkoxy, and phenoxy groups in the compound can be substituted, but the unsubstituted form is also one of the preferred forms of the present invention.

[0852] 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.

[0853] As R 12 The hydrocarbon group in the hydrocarbon group can be any one of aliphatic hydrocarbon group or aromatic hydrocarbon group, preferably an aromatic hydrocarbon group.

[0854] 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.

[0855] 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.

[0856] As R 12 The substituents in R are preferably monovalent substituents, such as halogen atoms. Furthermore, R... 12 In the case of aromatic hydrocarbon groups, alkyl groups can be used as substituents.

[0857] In 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.

[0858] In equation (T-1), m is 2 or more, containing more than 2 R. 2 In the case of two or more R 2 The structures can be the same or different.

[0859] In equation (T-1), 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.

[0860] 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(-*)=.

[0861] As specific examples of compounds represented by formula (T-1), compounds corresponding to I-5 to I-8 in the examples can be cited, but are not limited to these.

[0862] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of a specific resin. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0863] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of a specific resin. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0864] Other additives may include compounds described in paragraphs 0316 to 0358 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0865] <Characteristics of Resin Compositions>

[0866] The viscosity of the resin composition of the present invention can be adjusted by utilizing 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 1,000 mm... 2 If the thickness is above / s, it is easy to coat with the film thickness required for reinsertion insulation, for example, if it is 12,000 mm. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0867] <Restrictions on the substances contained in the resin composition>

[0868] 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.

[0869] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[0870] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained in the form of complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above-described range.

[0871] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0872] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The amount present as halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. 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.

[0873] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0874] 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-layer bottles with an inner wall formed of six layers of six different resins, or bottles with a seven-layer structure formed of six different resins, are also preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0875] <Cure of the resin composition>

[0876] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0877] The cured product of the present invention is a cured product obtained by curing a resin composition.

[0878] 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 cured form of the resin composition is not particularly limited, and can be film-shaped, rod-shaped, spherical, granular, etc., depending on the application. In this invention, the cured form is preferably film-shaped. Through patterning of the resin composition, the shape of the cured form can also be selected according to applications such as forming a protective film on a wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, or imparting heat dissipation. The film thickness of the cured form (the film formed by the cured form) is preferably 0.5 μm or more and 150 μm or less.

[0879] The shrinkage rate during curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated by the following formula.

[0880] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0881] <Characteristics of cured resin compositions>

[0882] 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 sometimes results in a cured product with excellent mechanical properties.

[0883] 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.

[0884] 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.

[0885] <Preparation of Resin Compositions>

[0886] 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.

[0887] Examples of mixing methods include mixing using stirring blades, mixing using a ball mill, and mixing by rotating a tank.

[0888] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0889] 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. Regarding the filter pore size, it 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. Filters that have been pre-cleaned with an organic solvent can be used. In the filtration process, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, an HDPE filter with a 1 μm pore size can be used as the first stage, and an HDPE filter with a 0.2 μm pore size can be used as the second stage, and the two can be connected in series. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, it can be a circulating filtration. Furthermore, pressure filtration can be performed. When pressure filtration is performed, the pressure applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0890] In addition to filtration using filters, impurities can also be removed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0891] After filtration, the resin composition filled in the bottle can be degassed under reduced pressure.

[0892] (Method for manufacturing solidified products)

[0893] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[0894] A more preferred method for manufacturing a cured material is to include 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.

[0895] The method for manufacturing the cured material is particularly preferred to include at least one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[0896] Furthermore, the method for manufacturing the cured material is preferably to include the above-described film formation process and the process of heating the film.

[0897] The following is a detailed explanation of each process.

[0898] <Membrane Formation Process>

[0899] The resin composition of the present invention can be used in a film forming process in which it is applied to a substrate to form a film.

[0900] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[0901] [Substrate]

[0902] The type of substrate can be appropriately determined 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 substrates with a metal layer formed by electroplating or vapor deposition); paper; SOG (Spin-On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In particular, semiconductor substrates are preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[0903] Layers such as a sealing layer or an oxide layer formed of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[0904] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[0905] 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.

[0906] As a substrate, a plate-like material can be used, and a panel-like substrate (substrate) is preferred.

[0907] When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer formed by curing) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0908] As a method for applying the resin composition to a substrate, coating is preferred.

[0909] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating 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 applicable method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating is preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating is preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0910] Furthermore, it is also possible to apply a method for transferring a coating that has been applied and formed on a temporary support in advance by the above-described application method onto a substrate.

[0911] 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 may preferably be used.

[0912] 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.

[0913] Alternatively, a pre-wetting process can be used: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0914] <Drying Process>

[0915] After the film formation process (layer formation process), in order to remove the solvent, the above-mentioned film can be used for a process of drying the formed film (layer) (drying process).

[0916] 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.

[0917] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0918] 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 be performed under reduced pressure. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0919] <Exposure Process>

[0920] The above-mentioned film can be used in an exposure process that selectively exposes the film.

[0921] The method for manufacturing a cured material may include an exposure process that selectively exposes a film formed by a film forming process.

[0922] Selective exposure refers to exposing only a portion of the film. Furthermore, by selectively exposing the film, exposed areas (exposed portions) and unexposed areas (non-exposed portions) are formed on the film.

[0923] The exposure amount is not particularly limited as long as it is sufficient to cure the resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm based on the exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[0924] The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0925] 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), and wide wavelengths (gamma, h, i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet (EUV) (wavelength 13.6nm), (6) electron beams, and (7) second harmonic 532nm and third harmonic 355nm of YAG lasers. Regarding the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and from the viewpoint of exposure sensitivity, exposure using i-rays is more preferred.

[0926] There is no particular limitation on the exposure method, as long as at least a portion of the film formed by the resin composition of the present invention is exposed, but examples include exposure using a photomask, exposure using direct laser imaging, etc.

[0927] <Post-exposure heating process>

[0928] The above-mentioned film can be used in a process of heating after exposure (post-exposure heating process).

[0929] 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.

[0930] The post-exposure heating process can be performed after the exposure process and before the development process.

[0931] The heating temperature in the post-exposure heating process is preferably 50–140°C, more preferably 60–120°C.

[0932] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0933] 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.

[0934] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0935] There are no particular limitations on the heating method used in the post-exposure heating process; known heating plates, ovens, infrared heaters, etc., can be used.

[0936] Furthermore, during heating, it is preferable to conduct the process in a low-oxygen environment by circulating inactive gases such as nitrogen, helium, or argon.

[0937] <Developing Process>

[0938] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0939] That is, the method for manufacturing the cured product of the present invention may include a developing step of developing a film exposed by an exposure step to form a pattern using a developing solution.

[0940] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0941] Here, the development process that removes the non-exposed portions of the film is called negative development, and the development process that removes the exposed portions of the film is called positive development.

[0942] [Developing solution]

[0943] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0944] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is preferred. In the total mass of the developer, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0945] When the developer contains an organic solvent, compounds described in paragraph 0387 of International Publication No. 2021 / 112189 may be used as the organic solvent. This content is incorporated into this specification. Furthermore, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., are preferably examples of alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., are preferably examples of amides.

[0946] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, more preferably a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and especially preferably a developer containing cyclopentanone.

[0947] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[0948] The developer may further contain other ingredients.

[0949] Other components include, for example, well-known surfactants or well-known defoamers.

[0950] [Method for supplying developer]

[0951] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include immersing the substrate with the film formed in the developer, swirling immersion development using a nozzle to supply the developer to the film formed on the substrate, or continuous supply of developer. There are no particular restrictions on the type of nozzle, such as straight nozzles, spray nozzles, and mist nozzles.

[0952] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, the method of supplying developer with a straight nozzle or the method of continuous supply with a spray nozzle is preferred. From the viewpoint of developer penetration into the image area, the method of supplying with a spray nozzle is more preferred.

[0953] Furthermore, the following steps can be adopted: after continuously supplying developer with a straight nozzle, rotating the substrate to remove developer from the substrate, rotating and drying, and then continuously supplying developer with a straight nozzle again, rotating the substrate to remove developer from the substrate, or repeating this step multiple times.

[0954] Methods for supplying developer in the developing process include: a process of continuously supplying developer to a substrate; a process of keeping the developer in a substantially static state on the substrate; a process of vibrating the developer on the substrate using ultrasound or the like; and processes that combine these methods.

[0955] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18°C ​​to 30°C.

[0956] In the developing process, the pattern can be further cleaned (rinsed) using a rinsing solution after treatment with the developing solution. Alternatively, the rinsing solution can be supplied before the developing solution in contact with the pattern has completely dried.

[0957] [Rinse solution]

[0958] 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.

[0959] As an organic solvent in the rinsing solution, examples of organic solvents can be the same as those exemplified in the developing solution described above.

[0960] 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 with low solubility in the pattern compared to the organic solvent contained in the developing solution.

[0961] When the rinsing solution contains an organic solvent, one or more organic solvents may be used. Preferably, the organic solvent is cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME; more preferably, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME; and even more preferably, cyclohexanone or PGMEA.

[0962] 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 can be 100% by mass, relative to the total mass of the rinsing solution.

[0963] The rinsing solution may further contain other ingredients.

[0964] Other components include, for example, well-known surfactants or well-known defoamers.

[0965] [Method for supplying flushing fluid]

[0966] 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 filling the container, supplying the rinsing liquid to the substrate by spraying, and continuously supplying the rinsing liquid to the substrate using a straight nozzle.

[0967] From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, methods for supplying rinsing fluid include spray nozzles, straight nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred. From the perspective of the penetrability of the rinsing fluid to the image area, a supply method using a mist nozzle is even more preferred. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles.

[0968] 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 through a spray nozzle.

[0969] As a method for supplying rinsing fluid in the rinsing process, it is possible to employ a process of continuously supplying rinsing fluid to the substrate, a process of maintaining the rinsing fluid on the substrate in a substantially static state, a process of vibrating the rinsing fluid on the substrate using ultrasound or the like, and a process that combines these methods.

[0970] 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.

[0971] <Heating Process>

[0972] The pattern obtained through the developing process (the pattern after rinsing during the washing process) can be used in a heating process for heating the pattern obtained through the developing process.

[0973] 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.

[0974] 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.

[0975] During the heating process, resins such as polyimide precursors are cyclized to form resins such as polyimide.

[0976] Furthermore, crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed.

[0977] The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, and even more preferably 160 to 250°C, especially preferably 160 to 230°C.

[0978] 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.

[0979] In the heating process, heating is preferably carried out from the initial temperature to the maximum heating temperature at a heating rate of 1 to 12°C / min. More preferably, the heating rate is 2 to 10°C / min, and even more preferably 3 to 10°C / min. Setting the heating rate to 1°C / min or more ensures productivity while preventing excessive evaporation of acid or solvent; setting the heating rate to 12°C / min or less reduces residual stress in the cured product.

[0980] Furthermore, in the case of an oven capable of rapid heating, the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0981] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the dried film (layer) is preferred; for example, it is preferably started at a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0982] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0983] In particular, when forming a multilayered laminate, from the viewpoint of interlayer tightness, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher.

[0984] The upper limit of the above heating temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

[0985] Heating can be performed in stages. For example, the following steps can be performed: increasing the temperature from 25°C to 120°C at a rate of 3°C / minute, holding at 120°C for 60 minutes, and then increasing the temperature from 120°C to 180°C at a rate of 2°C / minute, holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is preferable to perform the treatment while irradiating with ultraviolet light. This pretreatment process can improve the properties of the membrane. The pretreatment process can be performed in a short time, approximately 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be divided into two or more stages; for example, the first stage of the pretreatment process can be performed in the range of 100–150°C, followed by the second stage of the pretreatment process in the range of 150–200°C.

[0986] In addition, cooling can be performed after heating, and the preferred cooling rate at this time is 1 to 5°C / minute.

[0987] From the viewpoint of preventing the decomposition of specific resins, the heating process is preferably carried out in a low-oxygen environment by circulating inactive gases such as nitrogen, helium, or argon and by conducting the process under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0988] There are no particular limitations on the heating method used in the heating process. Examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0989] <Post-development exposure process>

[0990] The pattern obtained through the developing process (the pattern after rinsing during the washing process) can also replace the heating process described above, or, in addition to the heating process described above, can be used in a post-developing exposure process to expose the pattern after the developing process.

[0991] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step.

[0992] In the post-development exposure process, it can promote, for example, the cyclization reaction of polyimide precursors by photo-alkali-generating agents and the removal of acid-degrading groups by photo-acid-generating agents.

[0993] In the post-development exposure process, it is sufficient for at least a portion of the pattern obtained in the development process to be exposed, but preferably all of the pattern is exposed.

[0994] Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure process is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[0995] Regarding the post-development exposure process, for example, the light source used in the above-described exposure process can be used, and broadband light is preferred.

[0996] <Metal Layer Formation Process>

[0997] 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 also be used in the metal layer forming process for forming a metal layer on the pattern.

[0998] 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).

[0999] 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.

[1000] 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, methods such as photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations thereof 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 plating method, electrolytic plating using copper sulfate plating solution or copper cyanide plating solution can be cited.

[1001] The thickness of the metal layer, measured in the thickest part, is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

[1002] <Application>

[1003] Examples of applications in the manufacture of cured products to which the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress-relief films. Other applications include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or patterns formed on insulating films used for mounting purposes, such as those described above, through etching. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimides,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide & Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[1004] The method for manufacturing the cured product of the present invention or the cured product of the present invention can also be used for manufacturing offset printing plates or screen printing plates, etching of shaped parts, manufacturing of protective coatings and dielectric layers in the electronic field, especially in the microelectronic field.

[1005] (Laminated bodies and methods for manufacturing laminated bodies)

[1006] The laminate of the present invention refers to a structure having multiple layers formed by the cured product of the present invention.

[1007] A laminate is a laminate containing two or more layers formed by a solidified material, or it can be a laminate consisting of three or more layers.

[1008] Of the two or more layers formed by the cured material contained in the above-described laminate, at least one layer is formed by the cured material of the present invention. From the viewpoint of suppressing the shrinkage of the cured material or the deformation of the cured material accompanying the shrinkage, it is also preferable that all the layers formed by the cured material contained in the above-described laminate are formed by the cured material of the present invention.

[1009] That is, the manufacturing method of the laminate of the present invention preferably includes the manufacturing method of the cured product of the present invention, and more preferably includes the manufacturing method of the cured product of the present invention repeated multiple times.

[1010] The laminate of the present invention preferably comprises two or more layers formed of a cured material, and a metal layer is included between any of the layers formed of the cured material. The metal layer is preferably formed by the aforementioned metal layer forming process.

[1011] That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step between the methods for manufacturing multiple cured products, wherein a metal layer is formed on the layer formed by the cured product. The preferred embodiment of the metal layer forming step is as described above.

[1012] As a preferred example of the aforementioned laminate, a laminate containing at least three layers stacked sequentially: a layer formed of a first cured material, a metal layer, and a layer formed of a second cured material is a preferred example.

[1013] The layers formed by the first cured product and the layers formed by the second cured product are preferably both layers formed by the cured products of the present invention. The resin composition of the present invention used to form the layer formed by the first cured product and the resin composition of the present invention used to form the layer formed by the second cured product 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.

[1014] <Layering Process>

[1015] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[1016] The lamination process includes a series of steps on the surface of a pattern (resin layer) or metal layer, sequentially performing at least one of the following steps: (a) film formation (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step. This can be done by repeating at least one of (a) film formation step, (d) heating step, and post-development exposure step. Furthermore, (e) metal layer formation step can be included after at least one of (d) heating step and post-development exposure step. The lamination process can, of course, further appropriately include the aforementioned drying step, etc.

[1017] 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 is an example of a surface activation treatment. Details regarding surface activation treatment will be described later.

[1018] The above-mentioned lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[1019] For example, in a structure of resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, the resin layer is preferably configured to have 2 or more layers and 20 or fewer layers, and more preferably configured to have 2 or more layers and 9 or fewer layers.

[1020] The composition, shape, and film thickness of each of the above layers can be the same or different.

[1021] 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 to cover 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.

[1022] (Surface activation treatment process)

[1023] The preferred method for manufacturing the laminate of the present invention includes a surface activation treatment step that involves surface activation treatment of at least a portion of the metal layer and the resin composition layer.

[1024] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the above-mentioned 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.

[1025] Surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, the surface activation treatment is performed on at least a portion of the metal layer, and more preferably on a portion or all of the region of the metal layer on which 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 its surface can be improved.

[1026] The surface activation treatment is preferably performed on part or all of the exposed resin composition layer (resin layer). In this way, by performing a surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. In particular, when the resin composition layer has cured, such as during negative development, it is less likely to be damaged by the surface treatment, and adhesion is easily improved.

[1027] 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.

[1028] (Semiconductor devices and their manufacturing methods)

[1029] The present invention also discloses semiconductor devices comprising the cured or laminated material of the present invention.

[1030] 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.

[1031] As a specific example of using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer in a semiconductor device, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and... Figure 1 The records and information contained herein are included in this instruction manual.

[1032] Example

[1033] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, processing order, etc., shown in the following examples can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass measurements.

[1034] <Resin Synthesis>

[1035] [Synthetic Example PI-1: Synthesis of Polyimide (PI-1)]

[1036] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy) phthalic anhydride was dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 9.94 g (24.2 mmol) of 4,4'-isopropylidene bis(2-aminophenol), 5.235 g (24.2 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, and 0.629 g (5.764 mmol) of p-aminophenol were dissolved in 100 g of NMP. The solution was added dropwise to the above solution over 1 hour at a temperature of 10°C–25°C. After stirring at 25°C for 30 minutes, 10 g of toluene was added, and the reaction was carried out at 200°C for 4 hours while nitrogen was introduced. The mixture was then cooled to 25°C. Next, 13.2 g (86.4 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical were added to the cooled reaction solution. The mixture was reacted at 95°C for 15 hours, then cooled to 25°C and diluted with 200 g of tetrahydrofuran. The reaction solution was then added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and the polyimide resin was filtered. The resin was then re-slurryed with 1 L of water and filtered, followed by re-slurrying again with 1 L of methanol and filtering. The resin was then dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANCORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 liters of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried at 45°C under reduced pressure for 1 day to obtain polyimide (PI-1). The obtained polyimide (PI-1) had a weight-average molecular weight of 19,600 and a number-average molecular weight of 7,700. Polyimide (PI-1) is a resin having repeating units represented by the following formula (PI-1). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1037] The method for determining weight-average molecular weight is as follows.

[1038] Device: TOSHO HLC-8420 GPC

[1039] Tube Columns: Two TSK Gurdcolumn SuperAW-H and TSK Super AWM-H tubes connected in series.

[1040] Eluent: 10 mmol / L lithium bromide in N-methylpyrrolidone solution

[1041] Flow rate: 0.35 ml / min

[1042] Measurement wavelength: 275nm

[1043] Furthermore, the glass transition temperature of the resin was determined under the following conditions and recorded in the "Tg (°C)" column of the table described later. For subsequent resins, the method for determining the glass transition temperature (Tg) is the same.

[1044] <Measurement Conditions>

[1045] Using a differential scanning calorimeter, the temperature conditions of the solidified material were changed in the following order (1) to (4) under a nitrogen atmosphere to create a differential scanning calorimetry curve. The temperature at the intersection of the straight line extending the baseline of the low-temperature side of the differential scanning calorimetry curve to the high-temperature side and the tangent line drawn at the point where the curve gradient changes the most in the stage-change part of the glass transition can be determined.

[1046] (1) Increase the temperature from 25℃ to 300℃ at a rate of 10℃ / minute.

[1047] (2) Cool from 300℃ to 25℃

[1048] (3) Increase the temperature from 25℃ to 500℃ at a rate of 10℃ / minute.

[1049] (4) Cool from 500℃ to 25℃

[1050] [Chemical Formula 62]

[1051]

[1052] [Synthetic Examples PI-2 to PI-11: Synthesis of Polyimides (PI-2) to (PI-11)]

[1053] With appropriate changes to the raw materials, polyimides (PI-2) to (PI-11) were synthesized using the same method as in synthesis example PI-1. Polyimides (PI-2) to (PI-11) are resins having repeating units represented by the following formulas (PI-2) to (PI-11). 1 H-NMR spectroscopy determined the structure of each repeating unit. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of each resin are listed in the table below. In the structures described below, the subscript of the repeating unit indicates the molar ratio of each repeating unit.

[1054] [Chemical Formula 63]

[1055]

[1056] [Chemical Formula 64]

[1057]

[1058] [Chemical Formula 65]

[1059]

[1060] [Chemical Formula 66]

[1061]

[1062] [Chemical Formula 67]

[1063]

[1064] [Chemical Formula 68]

[1065]

[1066] [Chemical Formula 69]

[1067]

[1068] [Table 1]

[1069] weight average molecular weight number average molecular weight Tg (°C) PI-1 19,600 7,700 256 PI-2 22,500 10,100 250 PI-3 15,700 6,200 245 PI-4 11,500 5,800 235 PI-5 6,800 3,500 225 PI-6 8,900 4,300 220 PI-7 14,300 6,200 240 PI-8 12,500 5,800 232 PI-9 16,200 6,900 245 PI-10 11,500 5,200 252 PI-11 14,600 6,300 238

[1070] [Synthetic Example PA-1: Synthesis of Polyamide-Imine (PA-1)]

[1071] By changing the acid anhydride and diamine used as raw materials, polyamide-imide (PA-1) was synthesized using the same method as in synthesis example PI-1.

[1072] The obtained polyamide-imide (PA-1) has a weight-average molecular weight of 9,500 and a number-average molecular weight of 4,600. Polyamide-imide (PA-1) is a resin having repeating units represented by the following formula (PA-1). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1073] [Chemical Formula 70]

[1074]

[1075] [Synthetic Example PE-1: Synthesis of Polyesterimide (PE-1)]

[1076] By changing the acid anhydride and diamine used as raw materials, polyesterimide (PE-1) was synthesized using the same method as in synthesis example PI-1.

[1077] The obtained polyesterimide (PE-1) has a weight-average molecular weight of 11,200 and a number-average molecular weight of 5,800. Polyesterimide (PE-1) is a resin having repeating units represented by the following formula (PE-1). 1 H-NMR spectroscopy determined the structure of the repeating units. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[1078] [Chemical Formula 71]

[1079]

[1080] [Table 2]

[1081] weight average molecular weight number average molecular weight Tg (°C) PA-1 9,500 4,600 258 PE-1 11,200 5,800 243

[1082] [Synthetic Example SP-1: Synthesis of Polyimide Precursor (SP-1)]

[1083] 21.18 g (68.1 mmol) of 4,4'-oxophthalic dianhydride, 18.12 g (136 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 23.93 g (302 mmol) of pyridine, and 90 g of diethylene glycol dimethyl ether were mixed and stirred at 60 °C for 5 hours to prepare a diester of 4,4'-oxophthalic dianhydride and 2-hydroxyethyl methacrylate. The mixture was then cooled to -10 °C, and 17.12 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours to obtain a white precipitate of pyridinium hydrochloride. Next, a solution obtained by dissolving 8.86 g (44.2 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise to the mixture over 2 hours. Next, 10.0 g (217 mmol) of ethanol was added to the mixture, and the mixture was stirred for 2 hours. Then, 4 liters of water were added to precipitate the polyimide precursor resin, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, filtered again, and dried at 40°C for 2 days. Next, the dried resin was dissolved in 200 g of tetrahydrofuran, and 50 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added, and the mixture was stirred for 6 hours. Then, 4 liters of water were added to precipitate the polyimide precursor resin, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and dried under reduced pressure at 45°C for two days to obtain the polyimide precursor (SP-1). The obtained polyimide precursor SP-1 has a weight-average molecular weight of 10,500 and a number-average molecular weight of 3,400. The polyimide precursor (SP-1) is a resin having repeating units represented by the following formula (SP-1). 1 H-NMR spectroscopy determined the structure of the repeating unit.

[1084] [Chemical Formula 72]

[1085]

[1086] [Synthetic Examples SP-2 to SP-3: Synthesis of Polyimide Precursors (SP-2) to (SP-3)]

[1087] With appropriate changes to the raw materials, SP-2 to SP-3 were synthesized using the same method as SP-1.

[1088] The polyimide precursors (SP-2) and (SP-3) are resins having repeating units represented by the following formulas (SP-2) and (SP-3), respectively. 1 H-NMR spectroscopy determined the structure of the repeating unit.

[1089] [Chemical Formula 73]

[1090]

[1091] [Table 3]

[1092] weight average molecular weight number average molecular weight SP-2 16,600 7,000 SP-3 22,000 9,800

[1093] <Comparative Synthesis of Compound A-1>

[1094] In a drying reactor equipped with a flat-bottomed connector featuring a stirrer, condenser, and internal thermometer, 31.0 g (100 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 180.0 g of N-methylpyrrolidone (NMP) while removing moisture. Next, 44.4 g (100 mmol) of 4,4'-(hexafluoroisopropylidene) phthalic anhydride was added, and the mixture was stirred at 40°C for 2 hours. Then, 50 mL of toluene was added, and the temperature was raised to 180°C while nitrogen was flowing at a flow rate of 200 mL / min, and the mixture was stirred for 6 hours, then cooled to room temperature. Next, 130.0 g of N-methylpyrrolidone was added, diluted, and polyimide was precipitated in 2 liters of water. The water-polyimide mixture was then stirred at 2000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration. The filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. The resulting polyimide was then dried under reduced pressure at 40°C for 1 day to obtain A-1. A-1 had a weight-average molecular weight (Mw) of 30,100 and a number-average molecular weight (Mn) of 14,500.

[1095] pass 1 H-NMR spectroscopy confirmed that the structure of A-1 is the structure represented by the following formula (A-1).

[1096] [Chemical Formula 74]

[1097]

[1098] <Comparative Synthesis of Compound A-2>

[1099] In a drying reactor equipped with a flat-bottomed connector featuring a stirrer, condenser, and internal thermometer, 44.43 g (113.7 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 77.32 g (125.0 mmol) of 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl-1,3-dioxoisobenzofuran-5-carboxylic acid ester were added while removing moisture, along with 492.43 g of γ-butyrolactone. The mixture was stirred at 60 °C for 1.5 hours. Next, 50 mL of toluene was added, and the temperature was raised to 180 °C while nitrogen was flowing at a flow rate of 200 mL / min. The mixture was stirred for 3 hours and then cooled to room temperature. The obtained polymerization solution was diluted with acetone to prepare a diluent. This diluent was then added dropwise to a water / methanol mixture of 3:1, causing a white solid to precipitate. The resulting white solid was recovered and dried under vacuum at 120°C, yielding 108 g of polymer.

[1100] Next, 73.86 g (150.0 mmol equivalent of hydroxyl groups) of the polymer obtained above, 21.17 g (150.0 mmol) of 2-ethyl acrylate (hereinafter also referred to as AOI, manufactured by SHOWA DENKO KK), and 828.26 g of γ-butyrolactone (GBL) were added to a reaction vessel equipped with a stirrer and a cooling pipe. The temperature was then raised to 120°C while stirring, and the reaction was carried out for 6 hours. The resulting reaction solution was then diluted with acetone to prepare a diluent. This diluent was then added dropwise to a water / methanol mixture of 2:1, causing a white solid to precipitate. The white solid was recovered and dried under vacuum at 40°C to obtain 70.0 g of the polymer.

[1101] A-2 has a weight-average molecular weight (Mw) of 34,200 and a number-average molecular weight (Mn) of 12,800.

[1102] It is speculated that the structure of A-2 is such that the structure represented by the following formula (A-2) is the main component.

[1103] According to the H-NMR measurements, the crosslinking group incorporation rate was 55%.

[1104] [Chemical Formula 75]

[1105]

[1106] [Table 4]

[1107] weight average molecular weight number average molecular weight Tg (°C) A-1 30,100 14,500 230 A-2 34,200 12,800 245

[1108] <Examples and Comparative Examples>

[1109] In each embodiment, the components listed in the table were mixed to obtain each resin composition. Furthermore, in each comparative example, the components listed in the table were mixed to obtain each comparative composition.

[1110] Specifically, the content of each component recorded in the table is set as the amount (parts by mass) recorded in the "Amount Added" column of each column of the table.

[1111] The obtained resin composition and the comparative composition were pressure filtered using a polypropylene filter with a pore width of 0.5 μm.

[1112] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[1113]

[1114]

[1115] The detailed information of each component recorded in the table is as follows.

[1116] [Resin]

[1117] • PI-1 to PI-11: PI-1 to PI-11 synthesized in the above process

[1118] PA-1: PA-1 synthesized in the above process

[1119] PE-1: PE-1 synthesized in the above process

[1120] • A-1: ​​The above-mentioned synthetic product

[1121] PI-1 to PI-11, PA-1 and PE-1 are compounds corresponding to specific resins.

[1122] [Polymerizing compounds (all trade names)]

[1123] • B-1: SR-209: SR-209 (manufactured by Sartomer Company, Inc., melting point: below 25°C)

[1124] • B-2: ADPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: below 25°C)

[1125] • B-3: Light Acrylate 4EG-A (manufactured by KYOEISHA CHEMICAL CO., LTD., melting point: below 25°C)

[1126] • B-4: M-305 (manufactured by TOAGOSEI CO., LTD., melting point: below 25°C)

[1127] • B-5: 1,9-Nonanediol dimethacrylate (melting point: below 25°C)

[1128] • B-6: 1,9-Nonadiol diacrylate (melting point: below 25°C)

[1129] • B-7: Tris(2-Acryloyloxyethyl) Isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1130] [Solvent]

[1131] ·DMSO: Dimethyl sulfoxide

[1132] GBL: γ-Butyrolactone

[1133] NMP: N-methylpyrrolidone

[1134] ·γ-V: γ-valerolactone

[1135] The entry for "DMSO / GBL" in the table indicates that a solution was obtained by mixing DMSO and GBL at a mass ratio of 80:20.

[1136] [Polymerization initiators (all trade names)]

[1137] • OXE-01: IRGACURE OXE 01 (manufactured by BASF)

[1138] •OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[1139] •OXE-03: IRGACURE OXE 03 (manufactured by BASF)

[1140] ·Irgacure784 (BASF)

[1141] [Migration Inhibitor]

[1142] •E-1~E-7: Compounds with the following structures

[1143] [Chemical Formula 76]

[1144]

[1145] [Metal Adhesion Improver]

[1146] • F-1~F-3: Compounds with the following structures

[1147] [Chemical Formula 77]

[1148]

[1149] ·F-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1150] ·F-5: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1151] ·F-6: X-12-989MS (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1152] ·F-7: X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1153] [Polymerization inhibitor]

[1154] ·G-1: 1,4-Benzoylene

[1155] G-2: 4-Methoxyphenol

[1156] G-3: 1,4-Dihydroxybenzene

[1157] • G-4: Compounds with the following structures

[1158] [Chemical Formula 78]

[1159]

[1160] G-5: 2-Nitrosamino-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1161] [Metal complex]

[1162] ·H-1: TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1163] ·H-2: TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1164] ·H-3: TC-800 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1165] ·H-4: TC-810 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1166] H-5: Compounds with the following structure

[1167] H-6: Compounds with the following structure

[1168] H-7: Compounds with the following structure

[1169] [Chemical Formula 79]

[1170]

[1171] [Developing solution]

[1172] ·I-1: Huanjiyou Tong

[1173] ·I-2: Dimethylcyclohexylamine 5% cyclohexanone solution

[1174] ·I-3: N-[2-(dimethylamino)ethyl]methacrylamide 5% by mass PGMEA solution

[1175] [Rinse solution]

[1176] J-1: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1177] J-2: 10% by mass PGMEA solution of dimethylcyclohexylamine

[1178] J-3: N-[2-(dimethylamino)ethyl]methacrylamide 10% by mass PGMEA solution

[1179] <Evaluation>

[1180] [Evaluation of flatness]

[1181] In each embodiment and comparative example, a resin composition or a comparative composition was applied by spin coating onto a silicon wafer with copper wiring having a 1:1 L / S (linewidth and spacing) pattern with a height of 15 μm and a width of 20 μm and a taper angle of 85 degrees, forming a resin composition layer. The silicon wafer with the obtained resin composition layer applied was dried on a hot plate, resulting in a resin composition layer with a uniform thickness of approximately 20 μm at the spacing of the copper wiring on the silicon wafer.

[1182] Under nitrogen atmosphere, the above resin composition layer was heated at a heating rate of 10°C / min to the temperature recorded in the "Temperature" column of the "Curing Conditions" section of the table to obtain a cured product.

[1183] The depression X (μm) of the cured material in the spacing of the copper wiring was measured using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation), and evaluated according to the following criteria. The evaluation results are recorded in the "Flatness" column of the table.

[1184] Figure 1 The diagram shows a schematic cross-sectional view of a silicon wafer with a solidified material formed on it, where copper wiring has been formed. Figure 1 The silicon wafer 16 includes copper wiring 14, and a cured material 12 is formed on the silicon wafer 16. Here, the cured material 12 in the region of the silicon wafer 16 where the copper wiring 14 is not formed has a recess of 18 μm. The width W of the spacing portion of the copper wiring is 20 μm, and the cone angle θ of the copper wiring is 85°. The recess 18 can be observed, for example, as the difference between the total thickness h1 of the cured material at the center of the copper wiring and the thickness h2 of the cured material at the center of the spacing portion of the copper wiring.

[1185] The smaller the depression 18(X), the better the flatness, and therefore it is preferred. For example, the preferred evaluation is A, B or C.

[1186] -Evaluation Criteria-

[1187] A: X is below 1μm.

[1188] B: X exceeds 1μm and is below 2μm.

[1189] C:X exceeds 2μm and is below 3μm.

[1190] D:X exceeds 3μm.

[1191] [Evaluation of curing shrinkage (shrinkage rate)]

[1192] In each embodiment and comparative example, the resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer with the obtained resin composition layer applied was dried at 100°C for 5 minutes on a hot plate, resulting in a uniform, curable resin composition layer with a thickness of approximately 15 μm on the silicon wafer. The thickness of the curable resin composition layer was measured using a reflective spectrophotometer (FE-3000, manufactured by Otsuka Electronics Co., Ltd.), and this value was designated as "film thickness A". In any example, the measured film thickness A was 15 μm.

[1193] Next, using a stepper motor (Nikon NSR 2005 i9C) at 500mJ / cm 2 The entire surface of the obtained curable resin composition layer was exposed to i-rays using an exposure energy of [energy value missing].

[1194] The exposed curable resin composition layer (resin layer) was heated at a rate of 10°C / min under a nitrogen atmosphere. After reaching the temperature listed in the "Temperature" column of the "Curing Conditions" section of the table, it was heated for 3 hours and then cooled to 25°C to obtain a cured product. The film thickness of the cured product was measured using a reflective spectrophotometer (FE-3000, manufactured by Otsuka Electronics Co., Ltd.), and the value was taken as "film thickness B". The film shrinkage rate was calculated using the following formula.

[1195] Calculation formula: Shrinkage rate (%) = 100 - (film thickness B ÷ film thickness A × 100)

[1196] The evaluation should be conducted according to the following criteria, and the results should be recorded in the "Cure Shrinkage" column of the table. The smaller the shrinkage rate value, the better the cure shrinkage of the obtained composite layer.

[1197] Furthermore, in the example where the temperature recorded in the "Temperature" column of the "Curing Conditions" table is different from 230°C, the heating temperature was set to 230°C. Otherwise, the curing shrinkage was evaluated using the same method as described above, but the evaluation results were no different from those when heating was performed at the temperature recorded in the "Temperature" column of the "Curing Conditions" table.

[1198] -Evaluation Criteria-

[1199] A: The membrane shrinkage rate is less than 10%.

[1200] B: The membrane shrinkage rate is greater than 10% and less than 15%.

[1201] C: The membrane shrinkage rate is greater than 15% and less than 20%.

[1202] D: The membrane shrinkage rate is over 20%.

[1203] [Evaluation of chemical resistance]

[1204] By spin coating, the resin compositions or comparative compositions prepared in each example and comparative example were applied to a silicon wafer, thereby forming a resin composition layer. The silicon wafer with the obtained resin composition layer applied was dried on a hot plate at 100°C for 5 minutes, forming a resin composition layer with a uniform thickness of 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the resin composition layer on the silicon wafer was coated with 500 mJ / cm². 2The entire surface was exposed to the exposure energy, and the exposed resin composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 10°C / min. The temperature was then heated for 180 minutes at the temperature recorded in the "Temperature" column of the "Curing Conditions" section of the table to obtain a cured layer (resin layer) of the resin composition layer.

[1205] The obtained resin layer was immersed in the following solution under the following conditions, and the dissolution rate was calculated.

[1206] Solution: A mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution in a ratio of 90:10 (by mass).

[1207] Evaluation conditions: The resin layer was immersed in a solution at 75°C for 15 minutes. The film thickness change rate (100 - (film thickness after immersion / film thickness before immersion × 100)) was calculated from the film thickness before and after immersion. Regarding the film thickness, the film thickness was measured at 10 points on the coated surface using an ellipsometry (Foothill KT-22), and the arithmetic mean was used to determine the thickness.

[1208] The evaluation should be conducted according to the following criteria, and the results should be recorded in the "Chemical Resistance" column of the table. Generally speaking, the smaller the change in film thickness before and after immersion in the chemical solution, the better the chemical resistance.

[1209] Furthermore, in the example where the temperature recorded in the "Temperature" column of the "Curing Conditions" table is different from 230°C, the heating temperature was set to 230°C. Otherwise, the chemical resistance was evaluated using the same method as described above, but the evaluation results were no different from those obtained when heating was performed at the temperature recorded in the "Temperature" column of the "Curing Conditions" table.

[1210] -Evaluation Criteria-

[1211] A: The film thickness change rate is less than 10%.

[1212] B: The film thickness change rate is above 10% and below 20%.

[1213] C: The film thickness change rate exceeds 20% but is less than 40%.

[1214] D: The film thickness variation rate is over 40%.

[1215] [Evaluation of degassing properties]

[1216] In each embodiment and comparative example, a resin composition layer was formed by spin-coating the resin composition or the comparative composition onto a silicon wafer. The silicon wafer with the obtained resin composition layer applied was dried on a hot plate at 100°C for 5 minutes. A stepper (Nikon NSR 2005 i9C) was used at 500 mJ / cm².2 The entire surface of the obtained resin composition layer was exposed to I-rays at an exposure energy of [energy value missing]. After the exposure, the layer was developed for 60 seconds with the developer listed in the "Developer" column of the table, and rinsed for 30 seconds with the rinse solution listed in the "Rinse" column of the table.

[1217] The resin composition layer (resin layer) after rinsing was heated in a nitrogen atmosphere at a rate of 10°C / min until the temperature listed in the "Temperature" column of the "Curing Conditions" section of the table was reached, and then heated for 3 hours. The cured resin layer (cured product) was then immersed in a 4.9% by mass hydrofluoric acid aqueous solution and peeled off from the silicon wafer. 1–5 mg of the peeled film was weighed onto an aluminum tray, and the mass reduction rate was measured using a NETZSCH Japan kk TG-DTA2500 under the following conditions.

[1218] -Determination Conditions-

[1219] Under nitrogen atmosphere, the temperature conditions were changed in the following order (1) to (3), and the mass before (1) (mass A) and the mass after (3) (mass B) were measured. The mass reduction rate was calculated by the following formula.

[1220] (1) Increase the temperature from 25°C to 260°C at a rate of 10°C / minute, and maintain the temperature at 260°C for 15 minutes.

[1221] (2) Increase the temperature from 260℃ to 300℃ at a rate of 10℃ / minute.

[1222] (3) Cool to below 25°C

[1223] Mass reduction rate (%) = (1 - mass B / mass A) × 100

[1224] The evaluation should be conducted according to the following criteria, and the results should be recorded in the "Degassing" column of the table. Generally speaking, the lower the mass reduction rate, the better the degassing performance.

[1225] Here, the above exposure is omitted. Resin composition layers of three thicknesses are formed by applying resin compositions with thicknesses of 5 μm, 10 μm, or 20 μm respectively. After drying at 100°C for 5 minutes, the layers are heated at 230°C for 3 hours under nitrogen atmosphere to obtain cured products. The temperature conditions are changed in the following order (4) to (7), and the mass before (4) (mass C) and the mass after (7) (mass D) are measured. The mass reduction rate 2 is calculated by the following formula. As a result, the evaluation result of the film with the smallest mass reduction rate among the above three films is the same as the evaluation result recorded in the "degassing" column above.

[1226] Mass reduction rate 2 (%) = (1 - mass D / mass C) × 100

[1227] (4) Increase the temperature from 25℃ to 260℃ at a rate of 10℃ / minute.

[1228] (5) Keep at 260℃ for 15 minutes

[1229] (6) Increase the temperature from 260℃ to 300℃ at a rate of 10℃ / minute.

[1230] (7) Cool to below 25°C

[1231] Furthermore, in the evaluation of the above-mentioned mass reduction rate 2, the heating at 230°C for 3 hours was changed to heating at 170°C for 3 hours. Otherwise, the mass reduction rate 3 was measured in the same manner as mass reduction rate 2. As a result, the evaluation result of the membrane with the smallest mass reduction rate among the above three membranes was the same as the evaluation result recorded in the "degassing" column above.

[1232] -Evaluation Criteria-

[1233] A: The quality reduction rate is less than 2%.

[1234] B: The quality reduction rate is more than 2% but less than 5%.

[1235] C: The quality reduction rate is more than 5% but less than 8%.

[1236] D: The quality reduction rate exceeds 8%.

[1237] [Determination of glass transition temperature (1)]

[1238] Regarding the cured product obtained in the above degassing evaluation (the cured product before heating in the aluminum pan), the glass transition temperature was determined according to the following test conditions.

[1239] <Measurement Conditions>

[1240] Using a differential scanning calorimeter, the temperature conditions of the solidified material were changed in the following order (1) to (4) under a nitrogen atmosphere to create a differential scanning calorimetry curve. The temperature at the intersection of the straight line extending the baseline of the low-temperature side of the differential scanning calorimetry curve to the high-temperature side and the tangent line drawn at the point where the curve gradient changes the most in the stage-change part of the glass transition can be determined.

[1241] (1) Increase the temperature from 25℃ to 300℃ at a rate of 10℃ / minute.

[1242] (2) Cool from 300℃ to 25℃

[1243] (3) Increase the temperature from 25℃ to 500℃ at a rate of 10℃ / minute.

[1244] (4) Cool from 500℃ to 25℃

[1245] The evaluation shall be conducted in accordance with the following evaluation criteria, and the evaluation results shall be recorded in the “Tg(1)” column of the table.

[1246] Furthermore, in the example where the temperature recorded in the "Temperature" column of the "Curing Conditions" table is different from 230°C, the heating temperature was set to 230°C. Otherwise, the glass transition temperature was evaluated using the same method as described above, but the evaluation results were no different from those obtained when heating at the temperature recorded in the "Temperature" column of the "Curing Conditions" table.

[1247] -Evaluation Criteria-

[1248] A: The glass transition temperature of the cured product is above 250℃.

[1249] B: The glass transition temperature of the cured product is less than 250℃ and above 200℃.

[1250] C: The glass transition temperature of the cured product is less than 200℃.

[1251] [Determination of glass transition temperature (2)]

[1252] By spin coating, resin composition layers of three different thicknesses—5 μm, 10 μm, and 20 μm—were formed on silicon wafers. In the case of a 20 μm film thickness, the spin coating speed was set to 2000 rpm. In the case of a 10 μm film thickness, the solids concentration of the composition was diluted to 29% by mass using the solvent contained in each composition (solvents listed in the table), and the spin coating speed was set to 1500 rpm. In the case of a 5 μm film thickness, the solids concentration of the composition was diluted to 29% by mass using the solvent contained in each composition (solvents listed in the table), and the spin coating speed was set to 3000 rpm. Silicon wafers to which the obtained resin composition layers were applied were dried on a hot plate at 100°C for 5 minutes, thus forming the resin composition layer on the silicon wafers.

[1253] In a nitrogen atmosphere, the above-mentioned resin composition layer was heated at a rate of 10°C / min until it reached 170°C. This temperature was then maintained for 2 hours to obtain a cured product.

[1254] The cured material was immersed in a 4.9% (w / w) aqueous solution of hydrofluoric acid and then peeled off from the silicon wafer. The glass transition temperature of the obtained cured material was determined under the following conditions.

[1255] <Measurement Conditions>

[1256] Using a differential scanning calorimeter, the temperature conditions of the solidified material were changed in the following order (1) to (4) under a nitrogen atmosphere to create a differential scanning calorimetry curve. The temperature at the intersection of the straight line extending the baseline of the low-temperature side of the differential scanning calorimetry curve to the high-temperature side and the tangent line drawn at the point where the curve gradient changes the most in the stage-change part of the glass transition can be determined.

[1257] (1) Increase the temperature from 25℃ to 300℃ at a rate of 10℃ / minute.

[1258] (2) Cool from 300℃ to 25℃

[1259] (3) Increase the temperature from 25℃ to 500℃ at a rate of 10℃ / minute.

[1260] (4) Cool from 500℃ to 25℃

[1261] The evaluation shall be conducted in accordance with the following evaluation criteria, and the evaluation results shall be recorded in the “Tg(2)” column of the table.

[1262] -Evaluation Criteria-

[1263] A: The minimum glass transition temperature among the three thicknesses of cured products is above 230℃.

[1264] B: The minimum glass transition temperature of the cured products of the three thicknesses is less than 230℃ and above 200℃.

[1265] C: The minimum glass transition temperature of the cured material of the three thicknesses is less than 200℃.

[1266] <Example 101>

[1267] The resin composition used in Example 1 was applied in a layered manner to the surface of a resin substrate with a copper thin layer formed thereon using spin coating. After drying at 100°C for 4 minutes to form a resin composition layer with a film thickness of 20 μm, exposure was performed using a stepper (manufactured by Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 linewidth and spacing, and a linewidth of 10 μm). After exposure, heating was performed at 100°C for 4 minutes. Following the above heating, development was performed with cyclohexanone for 2 minutes, followed by rinsing with PGMEA for 30 seconds to obtain the pattern of the layer.

[1268] Next, under nitrogen atmosphere, the temperature was increased at a rate of 10°C / min until it reached 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer exhibits excellent insulation properties.

[1269] Furthermore, semiconductor devices were fabricated using these rewiring layers with interlayer insulating films, and normal operation was confirmed.

[1270] Symbol Explanation

[1271] 12-Currently cured material, 14-Copper wiring, 16-Silicon wafer, 18-Recess, H-Height of copper wiring, h1-Total thickness of the cured material and copper wiring in the central position of the copper wiring, h2-Thickness of the cured material in the central position of the spacing portion of the copper wiring, W-Width of the spacing portion of the copper wiring, θ-Tap angle of the copper wiring.

Claims

1. A photosensitive resin composition comprising: The resin is a polyimide with polymerizable groups and a weight-average molecular weight of 5,000 or more and less than 30,000. Polymer compounds; and Photopolymerization initiator.

2. A photosensitive resin composition comprising: The resin is selected from at least one of the groups consisting of polyimides and their precursors; Polymer compounds; and Photopolymerization initiator, Of the three cured products with different thicknesses that underwent thermogravimetric analysis under the following testing conditions 1, at least one had a mass reduction rate of less than 5% by mass. The shrinkage rate before and after curing is less than 15%. Measurement conditions 1: A cured product was obtained by heating a film of the photosensitive resin composition formed on a silicon substrate with a thickness of 5 μm, 10 μm, or 20 μm at 230°C for 3 hours. The mass reduction rate of the cured product was measured when the temperature was increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then increased from 260°C to 300°C at a rate of 10°C / min. The mass reduction rate is calculated using the following formula A. Formula A: Mass reduction rate (%) = {1 - (mass of the membrane after heating at 300℃) / (mass of the membrane at 25℃)} × 100.

3. The photosensitive resin composition according to claim 2, wherein, Among the three cured products with different thicknesses that underwent thermogravimetric analysis under the following measurement conditions 2, at least one product had a mass reduction rate of less than 5% by mass. Measurement condition 2: A cured product was obtained by heating a film of the resin composition, on which the resin composition was formed with a thickness of 5 μm, 10 μm, or 20 μm, on a silicon substrate at 170°C for 2 hours. The mass reduction rate of the cured product was measured when the temperature was increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then increased from 260°C to 300°C at a rate of 10°C / min. The mass reduction rate is calculated using the following formula A. Formula A: Mass reduction rate (%) = {1 - (mass of the membrane after heating at 300℃) / (mass of the membrane at 25℃)} × 100.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein, The weight-average molecular weight of the resin is greater than 10,000 and less than 25,000.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein, The resin composition satisfies the following condition 1. Condition 1: A cured product was obtained by heating a film of the resin composition, on which the resin composition was formed with a thickness of 15 μm, on a silicon substrate at 230°C for 3 hours. When the glass transition temperature of the cured product returned to 25°C, as determined by differential scanning calorimetry, the glass transition temperature was 180°C to 260°C.

6. The photosensitive resin composition according to any one of claims 1 to 3, wherein, The melting point of the polymeric compound is below 25°C.

7. The photosensitive resin composition according to any one of claims 1 to 3, wherein, The content of the polymeric compound is 1 to 40 parts by mass relative to 100 parts by mass of the resin composition.

8. The photosensitive resin composition according to any one of claims 1 to 3, wherein, The glass transition temperature of the resin is 180℃~260℃.

9. The photosensitive resin composition according to any one of claims 1 to 3, wherein, The resin comprises repeating units represented by the following formula (1-1). In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of these groups independently represents an organic group with a polymerizable group, where m represents an integer from 0 to 4 and n represents an integer greater than 1.

10. The photosensitive resin composition according to claim 9, wherein, The X 1 and Y 1 Each of these is an organic group that independently contains an organic group with a structure formed by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-10). In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group. 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 be optionally bonded to form a ring structure. In equation (V-8), R X5 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

11. The photosensitive resin composition according to claim 9, wherein, The R 1 For the group represented by formula (R-1), In equation (R-1), L 1 Z represents the linking group with a valence of a² + 1. 1 A represents an aromatic group or a cyclic aliphatic group. 1 Indicates a polymerizable group, a1 indicates 0 or more and Z 1 Integers below the largest substitution base, a2 represents integers above 1, and * represents X in equation (1-1). 1 Or Y 1 The bonding sites.

12. The photosensitive resin composition according to any one of claims 1 to 3, used to form an insulating component.

13. The photosensitive resin composition according to any one of claims 1 to 3, used for forming an interlayer insulating film for a rewiring layer.

14. A cured product formed by curing the photosensitive resin composition according to any one of claims 1 to 3.

15. A laminate comprising two or more layers formed of the cured material of claim 14, wherein a metal layer is included between any of the layers formed of the cured material.

16. A method for manufacturing a cured material, comprising a film forming step of applying the photosensitive resin composition of any one of claims 1 to 3 onto a substrate to form a film.

17. The method for manufacturing a cured product according to claim 16, comprising: The exposure process selectively exposes the film; and In the developing process, the film is developed using a developing solution to form a pattern.

18. The method for manufacturing a cured material according to claim 16, comprising a heating step of heating the film at 50°C to 450°C.

19. A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in claim 16.

20. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in claim 16.

21. A semiconductor device comprising the cured material of claim 14.

Images