Laminate and method for producing laminate

Abstract

Provided are a laminate and a method for manufacturing the laminate, the laminate being provided with: a sealing layer including a member having a circuit and a sealing material; a rewiring layer (A) that is in contact with one surface of the sealing layer and is connected to the circuit of the component; and a re-wiring layer B that is in contact with the other surface of the sealing layer and is not directly connected to the circuit of the component, the re-wiring layer A and the re-wiring layer B are formed so as to be electrically connectable to another component, the re-wiring layer A includes an insulating pattern A and a conductive pattern A that is present between the insulating patterns A, and the conductive pattern A is formed so as to be electrically connectable to another component. The rewiring layer B includes an insulating pattern B and a conductive pattern B present between the insulating patterns B. The insulating pattern A is composed of a composition, and the mass reduction rate of a cured product obtained by curing the composition at 230 DEG C for 3 hours is 10% or less when the cured product is held at 250 DEG C for 1 hour.

Description

Technical Field

[0001] This invention relates to a laminate and a method for manufacturing a laminate. Background Technology

[0002] In modern times, semiconductor packaging is used in mobile phones, tablet computers, and various other electronic devices. Semiconductor packaging refers to the housing used to protect delicate semiconductor chips or electronic circuits from external environmental influences and to mount them onto a substrate such as a printed circuit board. Semiconductor packaging has the function of transmitting signals generated from the aforementioned components to other devices and transmitting signals from other devices to the aforementioned components.

[0003] In mobile phones, tablet terminals, and other electronic devices, there is a growing trend towards miniaturization, weight reduction, and multifunctionality. To meet these demands, there are also requirements for further miniaturization, high integration, and high-density mounting in semiconductor packaging, and advancements in wiring technology, such as the use of rewiring layers, are expected.

[0004] For example, Patent Document 1 describes a semiconductor package comprising: a semiconductor die; a sealing material sealing the semiconductor die; a connector disposed on the sealing material; a redistribution conductive layer disposed on the sealing material and in contact with the connector, and having a first conductive pad disposed between the sealing material and the connector; a second conductive pad in contact with the redistribution conductive layer; and a semiconductor component electrically connected to the second conductive pad. The first conductive pad is disposed at a lower height than the second conductive pad. A first interlayer dielectric layer is disposed on the semiconductor die and the redistribution conductive layer, and the first interlayer dielectric layer includes an opening, a portion of which is occupied by the first conductive pad and the first electrical connector. The second and third interlayer dielectric layers are disposed... On a semiconductor die and under the first interlayer dielectric layer, a third conductive pad is disposed on the second interlayer dielectric layer, covered by the first interlayer dielectric layer, embedded in the second interlayer dielectric layer, and disposed on the third interlayer dielectric layer. It has a bridging structure connecting the first conductive pad and the third conductive pad. The bridging structure includes a first conductive via, a routing line, and a second conductive via. The via and the first conductive via directly connect the first conductive pad and the routing line. The routing line directly connects the first conductive via and the second conductive via. The second conductive via directly connects the routing line and the third conductive pad. The bottom surface of the entire routing line is in direct contact with the top surface of the third interlayer dielectric layer.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: U.S. Patent Application Publication No. 2023 / 0089795 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] In the context of laminates used in semiconductor packages and similar applications employing rewiring layers, excellent reliability over extended periods is required. Reliability refers to the property of consistently maintaining required performance characteristics such as insulation and adhesion, particularly the property of maintaining these characteristics even after accelerated testing under conditions of high temperature and high humidity.

[0010] The purpose of this invention is to provide a laminate with excellent reliability over a long period of time and a method for manufacturing the above-mentioned laminate.

[0011] means for solving technical problems

[0012] The following are examples of representative embodiments of the present invention.

[0013] <1> A layered body, comprising:

[0014] A sealing layer, which includes components with circuitry and sealing material;

[0015] Rewiring layer A, which contacts one side of the aforementioned sealing layer and is connected to the circuitry of the aforementioned component; and

[0016] The rewiring layer B contacts the other side of the aforementioned sealing layer but is not directly connected to the circuitry of the aforementioned component.

[0017] The aforementioned rewiring layer A and rewiring layer B are configured to be electrically connected to other components.

[0018] The aforementioned rewiring layer A includes an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A.

[0019] The aforementioned rewiring layer B includes an insulating pattern B and a conductive pattern B existing between the patterns of the insulating pattern B.

[0020] The above-mentioned insulating pattern A is composed of the following composition, which is cured at 230°C for 3 hours and the mass reduction rate of the cured product when held at 250°C for 1 hour is less than 10%.

[0021] <2> According to the laminated body described in <1>, wherein,

[0022] The aforementioned components with circuitry are functional dies.

[0023] <3> According to the laminate described in <2>, it also has functional grains that are electrically connected to the above-mentioned redistribution layer A.

[0024] <4> According to the laminated body described in <1>, wherein,

[0025] The aforementioned component with circuitry is a wiring layer, and the stack also includes two or more semiconductor devices electrically connected to the aforementioned rewiring layer A.

[0026] <5> The laminate according to any one of <1> to <4> further comprises a circuit component including wiring and an insulating layer, the circuit component being connected to the aforementioned rewiring layer B.

[0027] <6> The laminate according to any one of <1> to <5>, wherein,

[0028] The aforementioned rewiring layer A and rewiring layer B are connected via wiring.

[0029] <7> The laminate according to any one of <1> to <6>, wherein,

[0030] The aforementioned rewiring layer A comprises two or more layers consisting of the aforementioned insulating pattern A and the aforementioned conductive pattern A.

[0031] <8> The laminate according to any one of <1> to <7>, wherein,

[0032] The conductive pattern A mentioned above includes a line pattern, and the minimum line width of the line pattern is 0.1 to 10 μm.

[0033] <9> The laminate according to any one of <1> to <8>, wherein,

[0034] The thickness of the aforementioned rewiring layer A is 1–100 μm.

[0035] <10> The laminate according to any one of <1> to <9> has a barrier layer in at least a portion of the conductive pattern A.

[0036] <11> The laminate according to any one of <1> to <10> further includes a connecting member A on the side of the rewiring layer A that is different from the side that contacts the sealing layer.

[0037] <12> According to the laminated body described in <11>, wherein,

[0038] The aforementioned connecting component A is roughly spherical in shape.

[0039] <13> According to the laminated body described in <12>, wherein,

[0040] The height of the aforementioned connecting component A is less than 50 μm.

[0041] <14> According to the laminated body described in <11>, wherein,

[0042] The aforementioned connecting component A is roughly cylindrical.

[0043] <15> According to the laminated body described in <14>, wherein,

[0044] The height of the aforementioned connecting component A is less than 20 μm.

[0045] <16> According to the laminated body described in <11>, wherein,

[0046] The aforementioned connecting component A includes a bonding pad structure with an average diameter of less than 5 μm.

[0047] <17> A method for manufacturing a laminate, comprising:

[0048] In the sealing layer forming process, a component with circuitry is embedded in a sealing material to form a sealing layer in which the circuitry of the component is exposed on one side and not exposed on the other side.

[0049] In the process of forming the rewiring layer A, a rewiring layer A comprising an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A are formed on the surface of the sealing layer that exposes the circuit; and

[0050] In the process of forming the rewiring layer B, a rewiring layer B is formed on the surface of the sealing layer that does not expose the circuit, comprising an insulating pattern B and a conductive pattern B existing between the patterns of the insulating pattern B.

[0051] The mass reduction rate when the above insulation pattern A1 is maintained at 250°C for 1 hour is less than 10%.

[0052] <18> According to the method for manufacturing the laminated body described in <17>, wherein,

[0053] The aforementioned components with circuitry are functional chips.

[0054] <19> According to the method for manufacturing the laminated body described in <17>, wherein,

[0055] The aforementioned component with circuitry is a wiring layer, and the manufacturing method of the stack further includes a step of bonding the aforementioned rewiring layer A to two or more functional grains.

[0056] <20> A method for manufacturing a laminate according to any one of <17> to <19>, wherein,

[0057] The above-mentioned rewiring layer A forming process includes the step of applying the composition for forming the insulating pattern A onto the sealing material to form a film.

[0058] <21> According to the method for manufacturing the laminated body described in <20>, wherein,

[0059] The above-mentioned composition for forming insulating pattern A contains a resin having at least one repeating unit selected from the group consisting of repeating units represented by formula (2) and repeating units represented by formula (4).

[0060] [Chemical Formula 1]

[0061]

[0062] In equation (2), A 1 and A 2 Each 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 Each can independently represent a hydrogen atom or a monovalent organic group, R z It represents a hydrogen atom or a monovalent organic group.

[0063] [Chemical Formula 2]

[0064]

[0065] In equation (4), R 131 R represents a divalent organic group. 132 It represents a tetravalent organic group.

[0066] <22> The method for manufacturing the laminate according to <20> or <21>, wherein the composition for forming the insulating pattern A contains at least one solvent selected from γ-butyrolactone, dimethyl sulfoxide and N-methyl-2-pyrrolidone.

[0067] <23> A method for manufacturing a laminate according to any one of <20> to <22>, wherein,

[0068] The composition for forming the above-mentioned insulating pattern A also contains a polymeric compound.

[0069] <24> According to the manufacturing method of the laminated body described in <23>, wherein,

[0070] The aforementioned polymerizable compounds include compounds having two or more olefinic unsaturated bonds.

[0071] <25> A method for manufacturing a laminate according to any one of <20> to <24>, wherein,

[0072] The composition for forming the above-mentioned insulating pattern A also contains a photopolymerization initiator.

[0073] <26> According to the method for manufacturing the laminated body described in <25>, wherein,

[0074] The aforementioned photopolymerization initiator contains oxime compounds.

[0075] Invention Effects

[0076] According to the present invention, a laminate with excellent reliability over a long period of time and a method for manufacturing the above-mentioned laminate are provided. Attached Figure Description

[0077] Figure 1 This is a schematic cross-sectional view showing a specific example of connecting component A.

[0078] Figure 2 This is a schematic cross-sectional view illustrating an example of the laminate of the present invention.

[0079] Figure 3 This is a schematic cross-sectional view showing an example of rewiring layer A.

[0080] Figure 4 This is a schematic cross-sectional view illustrating an example of the laminate of the present invention.

[0081] Figure 5 This is a schematic cross-sectional view illustrating an example of a method for manufacturing a laminate according to the present invention.

[0082] Figure 6 This is a schematic cross-sectional view illustrating another example of a method for manufacturing a laminate according to the present invention.

[0083] Figure 7 This is a schematic cross-sectional view illustrating another example of a method for manufacturing a laminate according to the present invention. Detailed Implementation

[0084] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0085] In this specification, the numerical range represented by the symbol “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0086] In this specification, the term "process" means not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as they can achieve the intended function of the process.

[0087] In the designation of groups (atomic groups) in this specification, the designations without indicating whether they are substituted or unsubstituted include not only groups (atomic groups) without substituents, but also 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).

[0088] 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 bright-line spectra of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and active light or radiation such as electron beams.

[0089] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either of them, “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either of them, and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either of them.

[0090] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0091] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition. Furthermore, in this specification, solids concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0092] 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, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series as a column, 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 has low solubility, or where THF is unsuitable as the eluent, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm.

[0093] In this specification, when referring to the positional relationship of the layers constituting the laminate as "upper" or "lower," other layers may be located above or below the reference layer among the layers of interest. That is, a third layer or element may be sandwiched 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 (sealing layer) is referred to as "upper," or, in the presence of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, this vertical orientation is for ease of explanation; in practice, the "upper" direction in this specification may differ from the vertically upward direction.

[0094] In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to that component as each component in the composition. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0095] In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0096] In this specification, the preferred combination of methods is a more preferred method.

[0097] (Layered structure)

[0098] The laminate of the present invention (hereinafter also simply referred to as "laminate") comprises: a sealing layer including a component having a circuit and a sealing material; a redistribution layer A that contacts one side of the sealing layer and is connected to the circuit of the component; and a redistribution layer B that contacts the other side of the sealing layer and is not directly connected to the circuit of the component. The redistribution layers A and B are formed to be electrically connected to other components. The redistribution layer A includes an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A. The redistribution layer B includes an insulating pattern B and a conductive pattern B existing between the patterns of the insulating pattern B. The insulating pattern A is composed of a composition that, when cured at 230°C for 3 hours, results in a cured product with a mass reduction rate of 10% or less when held at 250°C for 1 hour.

[0099] The laminate of the present invention exhibits excellent reliability over a long period of time.

[0100] The mechanism by which the above effect is achieved is not yet clear, but it is hypothesized as follows. Normally, due to the escaping gas from the insulating pattern A, the insulating pattern shrinks over long-term use. However, this shrinkage is extremely small, and no peeling occurs between the insulating pattern A and the components it contacts, thus not immediately deteriorating the device's reliability. It is believed that this extremely small shrinkage creates undetectable microcracks within the insulating pattern. Over time, moisture penetrates these microcracks, causing partial corrosion of the components in contact with the insulating pattern A, i.e., the wiring metal, thereby impairing the long-term reliability of the device.

[0101] In this invention, the insulating pattern A is composed of a composition that, when cured at 230°C for 3 hours, results in a cured product with a mass reduction rate of less than 10% when held at 250°C for 1 hour. Therefore, it is believed that the insulating pattern A is less prone to shrinkage compared to conventional materials, does not produce microcracks, and inhibits moisture penetration. Consequently, the wiring metal is considered to be protected over a long period, resulting in improved long-term reliability.

[0102] The laminate of the present invention will now be described in detail.

[0103] <Sealing layer>

[0104] The sealing layer preferably comprises a sealing material and a component with circuitry, wherein the component with circuitry is embedded in the sealing material.

[0105] [Sealant]

[0106] As a sealing material, it is not particularly limited and known sealing materials can be used, but it is preferred to be a sealing material formed by curing a curing composition (curing adhesive).

[0107] As a curing composition, various curing compositions can be used, such as light-curing compositions (e.g., UV-curing), reaction-curing compositions (e.g., anaerobic or moisture-curing), and thermosetting compositions. Additionally, two-component mixtures and adhesive sheets can also be used.

[0108] As these curable compositions, curable resin compositions are preferred. Examples of resins used include epoxy resins, silicone resins, acrylic resins, phenolic resins, polyimide resins, imide resins, PVC (polyvinyl chloride) resins, PVB (polyvinyl butyral) resins, and EVA (ethylene vinyl acetate) resins.

[0109] In addition to resin, the curing resin composition may also contain other components such as fillers, polymerization initiators, curing agents, and desiccants. These components can be used without particular limitation, and are not limited to those previously known in the art.

[0110] [Components with circuitry]

[0111] As a component with circuitry, it is not particularly limited and can include functional chips, wiring layers, etc.

[0112] Preferably, the circuit or conductive component connected to the circuit in the component having circuitry is exposed on one side of the sealing layer, while neither the circuit nor the conductive component connected to the circuit is exposed on the other side.

[0113] Furthermore, it is preferable that the exposed circuit or the conductive component connected to the circuit is connected to the redistribution layer A described later.

[0114] Examples of conductive components include conductive pads.

[0115] Examples of materials for conductive components include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing at least one of these metals. Preferably, alloys containing copper, aluminum, or at least one of these metals are preferred. More preferably, copper or alloys containing copper are preferred. Copper is even more preferred.

[0116] -Functional grains-

[0117] In one aspect of the present invention, it is preferable that the circuit-equipped component described above is a functional chip.

[0118] In this invention, a functional chip refers to a chip assembled with circuitry, and specifically refers to a chip that displays storage, logic, and other functions.

[0119] The functional die is preferably a semiconductor chip. Functional dies are obtained, for example, by forming circuit patterns on a substrate such as silicon and monolithically processing them.

[0120] As a functional chip, it is not particularly limited, and examples include memory ICs, logic ICs, ASICs, and functional chips that further integrate these.

[0121] The number of functional grains sealed by the sealing layer is not particularly limited; it can be one or more. However, the method in which the sealing layer includes only one functional grain is also one of the preferred embodiments of the present invention.

[0122] The size of the functional grains is not particularly limited; for example, functional grains with one side of 100μm to 10cm can be cited.

[0123] - Wiring layer-

[0124] In another aspect of the invention, the circuit-featured component is preferably a wiring layer.

[0125] In this invention, the wiring layer refers to a layer consisting of simple wiring that does not exhibit storage, logic, or other functions.

[0126] The number of wiring layers sealed by the sealing layer is not particularly limited. There can be only one electrically independent wiring layer or multiple electrically independent wiring layers in the sealing layer. Electrical independence in the sealing layer means that it can be electrically connected through a structure outside the sealing layer (e.g., conductive pattern A in wiring layer A).

[0127] Wiring layers can be single layers or multiple layers.

[0128] -Conductive Part-

[0129] The sealing layer preferably also includes a conductive portion that connects one side of the sealing layer to the other side. This conductive portion is preferably included, for example, as a conductive through-hole that penetrates the sealing layer.

[0130] The aforementioned conductive portion connects, for example, redistribution layer A and redistribution layer B.

[0131] The thickness of the sealing layer is not particularly limited and can be determined by taking into account the thickness of components with circuitry, etc. However, for example, it is preferably 1μm to 500μm, and more preferably 10μm to 200μm.

[0132] <Rewiring Layer A>

[0133] The rewiring layer A is a layer that contacts one side of the sealing layer and is connected to the circuit of the component, and is a layer that includes an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A.

[0134] Here, the conductive pattern A is connected to the circuit-containing component in the sealing layer.

[0135] For example, one preferred method is to bring at least a portion of the conductive pattern A into contact with a circuit in a component with a circuit exposed on one side of the sealing layer, or with a conductive component connected to the circuit.

[0136] [Insulation Pattern A]

[0137] The volume resistivity of insulating pattern A at 25°C is not particularly limited, but 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. The upper limit is not particularly limited, but is preferably, for example, 1×10⁻⁶. 18 Below Ω·cm.

[0138] The insulating pattern A preferably includes a resin, and more preferably includes a polyimide.

[0139] Furthermore, the insulating pattern A is preferably a cured product of the composition for forming the insulating pattern A, which will be described later.

[0140] The insulating pattern A is composed of the following composition, and the cured product obtained by curing the composition at 230°C for 3 hours has a mass reduction rate of less than 10% when held at 250°C for 1 hour. The mass reduction rate is preferably less than 7.5%, and more preferably less than 5%.

[0141] The lower limit of the aforementioned mass reduction rate is not particularly limited, but is preferably 0% or higher.

[0142] Regarding the mass reduction rate, under nitrogen conditions, the temperature conditions were changed in the following order (1) to (2), the mass before (1) (mass A) and the mass after (2) (mass B) were measured, and the mass reduction rate was calculated by the following formula.

[0143] (1) Increase the temperature from 25°C to 250°C at a rate of 10°C / minute, and maintain the temperature at 250°C for 1 hour.

[0144] (2) Cool to 25°C

[0145] Mass reduction rate (%) = (1 - mass B / mass A) × 100

[0146] The aforementioned mass reduction rate can be adjusted by the structure and content of specific resins, polymeric compounds, etc., contained in the composition for forming the insulating pattern A, as described later.

[0147] The above-mentioned solidified material is produced by the following method.

[0148] First, the composition is coated onto a silicon wafer. The coating method is not particularly limited, but spin coating can be used. Furthermore, if it is difficult to form a film with a thickness of 15 μm (described later) using a single spin coating, multiple spin coatings can be performed. Even so, if it is difficult to form a film with a thickness of 15 μm using spin coating, an appropriate coating 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.

[0149] When the composition contains a solvent, drying is performed after the above coating. In this case, the distance from the silicon wafer surface to the dried film surface (i.e., film thickness) is set to 15 μm.

[0150] Drying is preferably carried out until the amount of solvent in the membrane reaches less than 0.5% by mass.

[0151] The drying conditions are not particularly limited and can be achieved by heating. Furthermore, when heating alone is insufficient for thorough drying, reduced pressure can be applied.

[0152] Drying can be carried out under atmospheric conditions. However, when the resin composition contains components that are easily modified by oxygen, it can also be carried out under conditions such as displacement by inert gases like nitrogen or under vacuum.

[0153] As a drying method, it is not particularly limited and can be carried out by a hot plate. However, when the above-mentioned pressure reduction, inert gas replacement, etc. are required, ovens with pressure reduction function or ovens with gas replacement function can also be used.

[0154] When drying is performed using heat, the heating temperature (drying temperature) can be, for example, 100°C. However, when it is difficult to dry at 100°C, the drying temperature can be appropriately changed between 70°C and 130°C, preferably between 90°C and 120°C, depending on the type of solvent contained in the resin composition.

[0155] When drying is performed using heat, the drying time (the time supplied to the above-mentioned heating temperature) can be, for example, 5 minutes. However, if it is difficult to dry within 5 minutes, the drying time can be appropriately changed between 30 seconds and 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the resin composition.

[0156] When drying is performed using heat, the heating rate is not particularly limited, and can be set to, for example, 5°C / min. When drying is difficult to perform at the above heating rate, the heating rate can be appropriately changed between 1 and 12°C / min or 2 and 10°C / min, depending on the type of solvent contained in the resin composition.

[0157] Using a stepper motor (Nikon NSR 2005 i9C), at 500 mJ / cm 2 The exposure energy exposes the entire surface of the coated film obtained by the above coating and drying as needed to i-rays. In addition to using i-rays from a stepper, exposure using lasers can also be applied, for example.

[0158] A cured product (cured resin) is prepared by heating the exposed composition layer (resin layer) at 230°C for 3 hours.

[0159] The above heating can be carried out in a nitrogen environment using an oven.

[0160] The pressure during the heating process is set to 1 atmosphere (101,325 Pa).

[0161] The heating rate described above can be set to, for example, 10°C / min. When drying is difficult at the above heating rate, the heating rate can be appropriately changed between 1 and 12°C / min or 2 and 10°C / min, depending on the type of solvent contained in the resin composition.

[0162] The heating time (exposure time to 230°C) in the above heating process is set to 3 hours.

[0163] The silicon wafer, which has been heated to form a cured resin, is immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured film is peeled off from the silicon wafer.

[0164] Regarding the peeled cured film, the mass reduction rate when kept at 250°C for 1 hour was determined using the method described above.

[0165] The elongation at break of the insulating pattern A is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0166] Furthermore, the elongation at break of the cured resin film is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0167] The upper limit of the above-mentioned elongation at break is not particularly limited, but is preferably below 100%.

[0168] For the determination of elongation at break, refer to the method described in JIS-K6251, using a tensile testing machine (TENSILON) at a crosshead speed of 300 mm / min, in an environment of 25°C and 65%RH (relative humidity).

[0169] The above-mentioned elongation at break can be adjusted according to the structure and content of the resin, polymeric compounds, etc. contained in the composition for forming the insulation pattern A, as described later.

[0170] The glass transition temperature of the insulating pattern A is preferably 215-275°C, more preferably 225-265°C, and even more preferably 235-255°C.

[0171] Regarding the glass transition temperature, it can be determined as follows: change the temperature conditions of the insulating pattern A in the order of (1) to (4) below, make a differential scanning calorimetry curve, and draw the temperature of the intersection point of the line drawn by 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 gradient of the curve in the step-like change part of the glass transition is the largest.

[0172] (1) Increase the temperature from 25°C to 300°C at a rate of 10°C / minute.

[0173] (2) Cooling from 300℃ to 25℃

[0174] (3) Increase the temperature from 25℃ to 500℃ at a rate of 10℃ / minute.

[0175] (4) Cooling from 500℃ to 25℃

[0176] The glass transition temperature described above can be adjusted according to the structure and content of specific resins, polymeric compounds, etc. contained in the composition for forming the insulating pattern A, as described later.

[0177] The coefficient of thermal expansion (CTE) of the insulating pattern A is preferably 20 to 80 ppm / K, more preferably 30 to 70 ppm / K, and even more preferably 40 to 60 ppm / K.

[0178] The coefficient of thermal expansion of insulating pattern A is determined by the following method.

[0179] Using the Discovery TMA thermomechanical analysis / coefficient of thermal expansion device manufactured by TA Instruments Japan Inc., the elongation (displacement) was measured while the temperature of the insulating pattern A was changed.

[0180] The heating and cooling conditions during the evaluation are set as follows (1) to (4).

[0181] (1) Heat from room temperature to 130°C at a heating rate of 5°C / minute.

[0182] (2) Cool down from 130℃ to 10℃ at a cooling rate of 5℃ / minute.

[0183] (3) Heat from 10℃ to 220℃ at a heating rate of 5℃ / minute.

[0184] (4) Allow to cool naturally to room temperature.

[0185] During the heating and cooling processes of (1) to (4) above, the elongation (displacement) of the sample was measured, and the elongation (displacement) of the sample in the length direction under the conditions of 25℃ and 125℃ in process (3) was calculated and divided by the temperature, which was used as the coefficient of thermal expansion.

[0186] For details of the determination method, please refer to the methods described in the examples below.

[0187] [Conductive pattern A]

[0188] The volume resistivity of conductive pattern A at 25°C is not particularly limited, but is preferably 1×10⁻⁶. -5 Ω·cm or less, more preferably 1×10 -6 Below Ω·cm, further preferably 1×10 -7 Below Ω·cm. The lower limit is not particularly limited, but is preferably, for example, 1×10⁻⁶. -11 Ω·cm or higher.

[0189] The preferred material for forming the conductive pattern A is a metal.

[0190] The metal is not particularly limited and existing metal types can be used, but examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing at least one of these metals. It is preferred to use alloys containing copper, aluminum or at least one of these metals, more preferably copper or alloys containing copper, and even more preferably copper.

[0191] The conductive pattern A preferably includes a line pattern. The line pattern includes, for example, a line and a space pattern in which the conductive pattern A is a line portion and the insulating pattern A is a space portion.

[0192] When the conductive pattern A includes a line pattern, the minimum line width of the line pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, and even more preferably 0.3 to 5 μm.

[0193] The conductive pattern A preferably has a barrier layer in at least a portion.

[0194] The conductive pattern A preferably has a barrier layer at at least at the interface between it and the insulating pattern A and between the rewiring layer A and the outside (i.e., the location where the conductive pattern A is exposed in the rewiring layer A).

[0195] By having a barrier layer, it is possible to suppress the transfer (migration) of materials (such as metals) that constitute the conductive pattern to other components such as the insulating pattern A or the sealing layer.

[0196] The components constituting the barrier layer are not particularly limited, but examples include tungsten, titanium, or alloys containing at least one of these metals.

[0197] Furthermore, the barrier layer can be formed using a metal with an ionization tensor lower than that of the material constituting the conductive pattern A.

[0198] [Structure of Re-wiring Layer A]

[0199] The rewiring layer A is formed to enable electrical connection with other components.

[0200] Specifically, the rewiring layer A can be configured such that the conductive pattern A is exposed on a surface different from the surface that contacts the sealing layer, or a barrier layer that contacts the conductive pattern A is exposed.

[0201] For example, the exposed conductive pattern A or barrier layer is connected to the connection component A described later, and then the wiring layer A is electrically connected to other components.

[0202] Furthermore, the rewiring layer A may include a conductive pad in the outermost layer (i.e., the layer furthest from the sealing layer).

[0203] Metal is preferred as the material for the conductive pad.

[0204] The metal is not particularly limited and existing metal types can be used, but examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing at least one of these metals. It is preferred to use alloys containing copper, aluminum or at least one of these metals, more preferably copper or alloys containing copper, and even more preferably copper.

[0205] When a conductive pad is present, the conductive pattern A is electrically connected to other components via the conductive pad.

[0206] Re-wiring layer A and re-wiring layer B are preferably connected via wiring.

[0207] Specifically, it is preferable that the conductive pattern A contained in the rewiring layer A and the conductive pattern B contained in the rewiring layer B are electrically connected via wiring, and more preferably that the conductive pattern A contained in the rewiring layer A and the conductive pattern B contained in the rewiring layer B are connected via the conductive portion contained in the aforementioned sealing layer.

[0208] The rewiring layer A may include two or more layers consisting of an insulating pattern A and a conductive pattern A.

[0209] Specifically, for example, it is preferable to include a layer consisting of 2 to 20 layers comprising an insulating pattern A and a conductive pattern A, and more preferably a layer consisting of 3 to 10 layers comprising an insulating pattern A and a conductive pattern A.

[0210] The thickness of the rewiring layer A is preferably 1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 1 to 20 μm.

[0211] <Rewiring Layer B>

[0212] The rewiring layer B is a layer that contacts the other side of the sealing layer and is not directly connected to the circuit of the component, and is a layer that includes an insulating pattern B and a conductive pattern B existing between the patterns of the insulating pattern B.

[0213] Here, "the conductive pattern B is not directly connected to the circuit-containing component in the sealing layer" means that the conductive pattern B is not in contact with the circuit in the circuit-containing component or the conductive component.

[0214] The conductive pattern B can be directly connected to the component with the circuit, or it can be electrically connected to the component with the circuit via other components. For example, it is preferable to electrically connect it to the component with the circuit via the conductive pattern A in the redistribution layer A.

[0215] For example, the following can be cited as one of the preferred embodiments of the present invention: the rewiring layer B is formed to contact the non-exposed surface of the circuit or conductive component connected to the circuit in the component having the sealing layer, and the rewiring layer A and the rewiring layer B are electrically connected via the conductive through-hole.

[0216] [Insulation Pattern B]

[0217] The volume resistivity of insulating pattern B at 25°C is not particularly limited, but 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. The upper limit is not particularly limited, but is preferably, for example, 1×10⁻⁶. 18 Below Ω·cm.

[0218] The insulating pattern B preferably includes a resin, and more preferably a polyimide.

[0219] Furthermore, the insulating pattern B is preferably a cured product of the composition for forming the insulating pattern A, which will be described later.

[0220] [Conductive pattern B]

[0221] The volume resistivity of conductive pattern B at 25°C is not particularly limited, but is preferably 1×10⁻⁶. -5 Ω·cm or less, more preferably 1×10 -6 Below Ω·cm, further preferably 1×10 -7Below Ω·cm. The lower limit is not particularly limited, but is preferably, for example, 1×10⁻⁶. -11 Ω·cm or higher.

[0222] The preferred material for forming the conductive pattern B is a metal.

[0223] The metal is not particularly limited and existing metal types can be used, but examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing at least one of these metals. It is preferred to use alloys containing copper, aluminum or at least one of these metals, more preferably copper or alloys containing copper, and even more preferably copper.

[0224] The conductive pattern B preferably includes a line pattern. The line pattern includes, for example, a line and a space pattern in which the conductive pattern B is a line portion and the insulating pattern B is a space portion.

[0225] When the conductive pattern B includes a line pattern, the minimum line width of the line pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, and even more preferably 0.3 to 5 μm.

[0226] The conductive pattern B preferably has a barrier layer in at least a portion.

[0227] The conductive pattern B preferably has a barrier layer at least at the interface between it and the insulating pattern B and between the rewiring layer B and the outside (i.e., the location where the conductive pattern B is exposed in the rewiring layer B).

[0228] By having a barrier layer, it is possible to suppress the transfer (migration) of materials (such as metals) that constitute the conductive pattern to other components such as the insulating pattern B or the sealing layer.

[0229] The components constituting the barrier layer are not particularly limited, but examples include tungsten, titanium, or alloys containing at least one of these metals.

[0230] Furthermore, the barrier layer can be formed using a metal with a lower ionization tendency than the material constituting the conductive pattern B.

[0231] [The composition of redistribution layer B]

[0232] The rewiring layer B is formed to enable electrical connection with other components.

[0233] Specifically, the rewiring layer B can be configured such that the conductive pattern B is exposed on a surface different from the surface that contacts the sealing layer, or a barrier layer that contacts the conductive pattern B is exposed.

[0234] For example, the exposed conductive pattern B or barrier layer is connected to the connection component B described later, and the wiring layer B is electrically connected to other components.

[0235] Furthermore, the rewiring layer B may include a conductive pad in the outermost layer (i.e., the layer furthest from the sealing layer).

[0236] Metal is preferred as the material for the conductive pad.

[0237] The metal is not particularly limited and existing metal types can be used, but examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing at least one of these metals. It is preferred to use alloys containing copper, aluminum or at least one of these metals, more preferably copper or alloys containing copper, and even more preferably copper.

[0238] When a conductive pad is present, the conductive pattern B is electrically connected to other components via the conductive pad.

[0239] The rewiring layer B may include two or more layers consisting of an insulating pattern B and a conductive pattern B.

[0240] Specifically, for example, it is preferable to include a layer consisting of 2 to 20 layers comprising an insulating pattern B and a conductive pattern B, and more preferably a layer consisting of 3 to 10 layers comprising an insulating pattern B and a conductive pattern B.

[0241] The thickness of the rewiring layer B is preferably 1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 1 to 20 μm.

[0242] <Other functional grains>

[0243] The laminate may also include other functional grains electrically connected to the redistribution layer A.

[0244] The preferred configurations for other functional grains are the same as those for functional grains included in the aforementioned sealing layer, except that they are not sealed by the sealing layer.

[0245] Other functional grains are preferably attached to surfaces of the redistribution layer A that are different from the surfaces that contact the sealing layer.

[0246] Specifically, other functional grains are preferably connected to the connecting component A, which will be described later.

[0247] When the aforementioned components with circuitry are the aforementioned functional grains, the laminate preferably also includes other functional grains electrically connected to the aforementioned redistribution layer A.

[0248] In this approach, the number of other functional grains can be one or more, preferably two or more, and even more preferably three or more.

[0249] In this approach, when there are more than two functional grains, the functional grains can be the same or different.

[0250] When the aforementioned component with circuitry is the aforementioned wiring layer, the laminate preferably also includes two or more other functional grains that are electrically connected to the aforementioned rewiring layer A.

[0251] In this approach, the number of other functional grains can be two or more, preferably five or more, and even more preferably ten or more.

[0252] In this approach, the functional grains can be the same or different.

[0253] <Circuit Components>

[0254] The laminate of the present invention may further include a circuit component connected to the aforementioned rewiring layer B and including wiring and an insulating layer.

[0255] Examples of circuit components include substrates on which circuits are formed. This circuit component may also have connection points with other components on a side different from the side connected to the rewiring layer B.

[0256] In this way, it is also easy to manufacture a device that further connects the laminate of the present invention to other substrates.

[0257] <Connecting Component A>

[0258] The laminate of the present invention may further include a connecting member A on the side of the rewiring layer A that is different from the side that contacts the sealing layer.

[0259] The connecting component A is preferably any one of the following: generally spherical, generally columnar, and having an average diameter of less than 5 μm.

[0260] Furthermore, the laminate of the present invention may include a barrier layer between the rewiring layer A and the connecting member A.

[0261] When the connecting component A is approximately spherical, the connecting component A is preferably a solder ball, a ball grid array (BGA) ball, or a C4 bump.

[0262] Figure 1 (a) is a schematic cross-sectional view of the connecting part A when it is roughly spherical in shape.

[0263] exist Figure 1 In (a), the connecting member A102 is connected to the conductive pattern A108 via the barrier layer 106, and the conductive pattern A108 is formed between the insulating patterns A104.

[0264] Regarding the insulating pattern A104 and the conductive pattern A108, although the description is simplified, it is actually preferable to further overlap the insulating pattern A104 and the conductive pattern A108 on the side opposite to the connecting member A102. Alternatively, the barrier layer 106 may not be provided. This is in... Figure 1 Same as in (b) and (c).

[0265] When the connecting part A is generally spherical, the material constituting the connecting part A is not particularly limited, but is preferably Sn, Pb, Ag, Cu, Ni, Bi or an alloy containing any of these.

[0266] When the connecting component A is approximately spherical, the height of the connecting component A is preferably less than 50 μm, more preferably 20 to 50 μm, and even more preferably 20 to 40 μm.

[0267] When the connecting component A is generally columnar, the connecting component A is preferably a column with a solder component at the top.

[0268] Figure 1 (b) is a schematic cross-sectional view of the connecting component A when it is roughly cylindrical.

[0269] exist Figure 1 In (b), the connecting component A102 is a component consisting of solder component 110 and post 112.

[0270] exist Figure 1 In (b), the solder component 110 is temporarily described as hemispherical, but the shape is not particularly limited and can be cylindrical or have a flat upper part.

[0271] exist Figure 1 In (b), the connecting member A102 is connected to the conductive pattern A108 via the barrier layer 106, and the conductive pattern A108 is formed between the insulating patterns A104.

[0272] When the connecting part A is generally columnar, the material constituting the column is not particularly limited, but is preferably Sn, Pb, Ag, Cu, Ni, Bi or an alloy containing any of these, and more preferably Cu.

[0273] When solder components are included, the materials constituting the solder components are not particularly limited, but Sn, Pb, Ni, Bi or alloys containing any of these are preferred.

[0274] When the connecting component A is generally columnar, the height of the connecting component A is preferably less than 20 μm, more preferably 10 to 20 μm, and even more preferably 10 to 15 μm.

[0275] When the connecting part A is a bonding pad structure with an average diameter of 5 μm or less, the connecting part A is preferably formed to be height aligned with the insulating pattern A, and the connecting part A and the insulating part are substantially flat.

[0276] Figure 1(c) is a schematic cross-sectional view of the connecting component A when it is a bonding pad structure with an average diameter of less than 5 μm.

[0277] exist Figure 1 In (c), the connecting part A102 is connected to the conductive pattern A108, which is formed between the insulating patterns A104.

[0278] When the connecting component A is a bonding pad structure with an average diameter of 5 μm or less, the material constituting the bonding pad structure is not particularly limited, but is preferably Sn, Pb, Ag, Cu, Ni, Bi or an alloy containing any of these, and more preferably Cu.

[0279] When the connecting component A is a bonding pad structure with an average diameter of 5 μm or less, the average diameter is 5 μm or less, preferably 1 to 5 μm, and more preferably 2 to 5 μm.

[0280] The average diameter mentioned above refers to the average diameter of the upper surface of the bonding pad structure. When the upper surface of the bonding pad structure is not circular, the average diameter refers to the average value of the equivalent diameter of a circle.

[0281] <Connecting Component B>

[0282] The laminate of the present invention may further include a connecting member B on a surface that is different from the surface that contacts the above-mentioned rewiring layer B and the surface that contacts the above-mentioned sealing layer.

[0283] The preferred configuration of the connecting component B is the same as that of the connecting component A, except that it is formed in the redistribution layer B.

[0284] <Specific examples of stacked structures>

[0285] Hereinafter, examples of specific embodiments of the laminates of the present invention will be shown in the figures for illustration, but the present invention is not limited to these examples.

[0286] Figure 2 This is a schematic cross-sectional view illustrating an example of the laminate of the present invention.

[0287] exist Figure 2 In the laminate 10, the sealing layer 12, the rewiring layer A14, and the rewiring layer B16 are included.

[0288] exist Figure 2 In this paper, the thickness of each layer has been appropriately changed to facilitate the confirmation of the attached drawings. In fact, for example, the thickness of the rewiring layer A14 is several tens to several hundredths of the thickness of the sealing layer 12, which may sometimes differ from the actual size.

[0289] The sealing layer 12 comprises a component 18 having a circuit, a sealing material 24, and a conductive through hole 26.

[0290] The component 18 having circuitry comprises a semiconductor component 22 and a circuit 20, the circuit 20 being connected to the redistribution layer A.

[0291] The component 18 with circuitry is described as a functional die including semiconductor component 22. However, when the component 18 with circuitry is a wiring layer, the component 18 with circuitry may consist only of circuitry 20, or semiconductor component 22 may not exist.

[0292] exist Figure 2 Although the illustration is omitted, the redistribution layer A14 includes an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A. Furthermore, the redistribution layer B16 includes an insulating pattern B and a conductive pattern B existing between the patterns of the insulating pattern B.

[0293] The conductive through-hole 26 is formed as a through-hole that penetrates the sealing layer and conducts conductive pattern A and conductive pattern B.

[0294] Here, circuit 20 is directly connected to redistribution layer A14, but circuit 20 is not directly connected to redistribution layer B16, but is connected via redistribution layer A.

[0295] Furthermore, in Figure 2 In this configuration, a connecting member A28 is formed on redistribution layer A, and a connecting member B30 is formed on redistribution layer B. Connecting member A28 is connected to conductive pattern A, and connecting member B30 is connected to conductive pattern B. Figure 2 In the text, connecting component A28 and connecting component B30 are described as being generally spherical, but as mentioned above, they can be other shapes such as generally cylindrical or mating pads.

[0296] Furthermore, in Figure 2 The connection component A28 is described in order to illustrate the positional relationship, but the connection component A28 can be formed before it is about to be joined with other functional grains, etc.

[0297] In addition, Figure 2 The connection component B30 is described in order to illustrate the positional relationship, but the connection component B30 can be formed before it is connected to other circuit components, etc.

[0298] According to this stack 10, the redistribution layer A14 can be connected to other functional chips via the connection member A28, and the redistribution layer B16 can be connected to circuit components via the connection member B30.

[0299] use Figure 3 right Figure 2 The details of the omitted redistribution layer A14 and connecting component A28 are explained below.

[0300] Figure 3This is a schematic cross-sectional view showing an example of a rewiring layer A14 with connecting component A28.

[0301] The rewiring layer A14 includes a conductive pattern A34 and an insulating pattern A32. Here, in Figure 3 In this document, the rewiring layer A14 is described as a rewiring layer comprising a total of four layers consisting of conductive patterns A and insulating patterns A. The surface 36 of the conductive pattern A, opposite to the connecting member A28, is... Figure 2 The circuit 20 in the middle is connected.

[0302] Figure 4 This is a schematic cross-sectional view showing another example of the laminate of the present invention.

[0303] Figure 4 Among the components marked with various symbols, those marked with... Figure 2 The components of the same symbol in the text are those that are identical to the symbol in the text. Figure 2 The same component as the one in the picture.

[0304] exist Figure 4 In the stack 50, two other functional grains 32 are connected to the redistribution layer A14, and the circuit component 34 is connected to the redistribution layer B16.

[0305] In this approach, the component 18 with circuitry can be a functional die including semiconductor component 22, and when the component 18 with circuitry is a wiring layer, it is natural that the component 18 with circuitry can be composed only of circuitry 20 and may not have semiconductor component 22.

[0306] Here, the space between the redistribution layer A14 and the functional grain 32 can be filled with a known underfill material.

[0307] Furthermore, the space between the rewiring layer B16 and the circuit component 34 can be filled with a known underfill material.

[0308] On the side of the circuit component 34 opposite to the redistribution layer B16, known connecting components such as solder balls may be further formed.

[0309] (Method for manufacturing laminates)

[0310] The method for manufacturing the laminate of the present invention includes: a sealing layer forming step, in which a component having a circuit is embedded in a sealing material to form a sealing layer in which the circuit of the component is exposed on one side and the circuit of the component is not exposed on the other side; a rewiring layer A forming step, in which a rewiring layer A including an insulating pattern A and a conductive pattern A existing between patterns of the insulating pattern A are formed on the side of the sealing layer in which the circuit is exposed; and a rewiring layer B forming step, in which a rewiring layer B including an insulating pattern B and a conductive pattern B existing between patterns of the insulating pattern B are formed on the side of the sealing layer in which the circuit is not exposed, wherein the mass reduction rate when the insulating pattern A is held at 250°C for 1 hour is 10% or less.

[0311] According to the manufacturing method of the laminate of the present invention, the laminate of the present invention described above can be obtained. That is, a laminate with excellent reliability over a long period of time can be obtained.

[0312] <Sealing layer formation process>

[0313] The method for manufacturing the laminate of the present invention includes a sealing layer forming step.

[0314] Through the sealing layer forming process, a sealing layer comprising a sealing material and a component having circuitry embedded in the sealing material can be obtained, wherein the sealing layer exposes the circuitry of the component on one side and does not expose the circuitry of the component on the other side.

[0315] In the sealing layer formation process, for example, the circuit-containing component can be disposed on a carrier wafer (pre-support) and the circuit-containing component can be embedded by applying the curable composition and curing it.

[0316] Furthermore, a known pre-bonding layer can also be formed on the carrier wafer.

[0317] For the application and solidification of these, well-known methods can be referenced.

[0318] The preferred embodiments of the curable composition and the components having circuitry are as described above.

[0319] The method in which the circuit-containing component is the aforementioned functional chip is also one of the preferred embodiments of the present invention.

[0320] Furthermore, the aforementioned component with circuitry is the aforementioned wiring layer, and the method for manufacturing the laminate of the present invention further includes the functional grain stacking process described later, which is also one of the preferred embodiments of the present invention.

[0321] Furthermore, during the sealing layer formation process, the surface can also be ground after the sealing material has cured.

[0322] Examples of the aforementioned grinding methods include chemical mechanical polishing (CMP) and physical polishing, but are not limited to these.

[0323] For example, by grinding the cured sealant on the side of a component with a circuit, the circuit of the component can be exposed on the surface of the sealant layer.

[0324] Furthermore, as a sealing layer forming process, any method known in the art can be used without particular restriction, as long as it is a method for forming a sealing layer.

[0325] Furthermore, grinding can be omitted during the sealing layer formation process, and the circuit can be exposed from the sealing layer simply by not sealing the surface of the circuit where the component with the circuit is located.

[0326] The preferred method for obtaining the sealing layer through the sealing layer formation process is the same as the preferred method for the sealing layer in the laminate of the present invention described above.

[0327] However, the conductive portion may not be formed in the sealing layer forming process. As described later, the conductive portion may be formed after at least one of the rewiring layer A forming process and the rewiring layer B forming process.

[0328] <Passivation layer formation process>

[0329] The manufacturing method of the laminate of the present invention may further include a passivation layer forming step after the sealing layer forming step.

[0330] The passivation layer formation process is preferably performed after the sealing layer formation process and before the rewiring layer A formation process.

[0331] Passivation layers are applied by coating a passivation film onto the surface of components containing circuitry. By forming a passivation layer, the effects of external gases on components containing circuitry, the adhesion of dust, and contamination caused by water or metal can sometimes be suppressed.

[0332] The material used as the passivation layer is not particularly limited, but examples include SiO2 and SiN. Additionally, resins such as polyimide can be used.

[0333] The coating method is not particularly limited and can be any known method. For example, when coating SiN, it can be done by CVD (Chemical Vapor Deposition).

[0334] <Re-wiring layer A formation process>

[0335] The method for manufacturing the laminate of the present invention includes a rewiring layer A forming step, wherein the rewiring layer A forming step forms a rewiring layer A comprising an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A on the surface of the sealing layer that exposes the circuit.

[0336] The rewiring layer A is formed on the surface of the sealing material that exposes the circuit via the rewiring layer A formation process. The preferred embodiment of the rewiring layer A is the same as the preferred embodiment of the rewiring layer A in the laminate of the present invention described above.

[0337] The process of forming the rewiring layer A preferably includes the step of applying the composition for forming the insulating pattern A onto the sealing layer to form a film (film forming process).

[0338] Furthermore, the rewire layer A forming process more preferably includes the above-mentioned film forming process, an exposure process for selectively exposing the film formed by the film forming process, and a developing process for developing the film exposed by the exposure process using a developing solution to form a pattern.

[0339] The re-line layer A forming process particularly preferably includes at least one of the above-described film forming process, the above-described exposure process, the above-described developing process, a heating process for heating the pattern obtained by the developing process, and a post-developing exposure process for exposing the pattern obtained by the developing process.

[0340] The details of each process are described below. Furthermore, details regarding the composition for forming insulating pattern A (hereinafter also referred to as the "composition") will be discussed later.

[0341] <Membrane Formation Process>

[0342] The process of forming the rewiring layer A preferably includes a film forming process of applying the composition onto the sealing layer to form a film.

[0343] As a method for applying the composition to the sealing layer, coating is preferred.

[0344] Specifically, methods used include dip coating, air knife coating, curtain coating, wire-wound bar coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating are preferred; from both the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are more preferred. By adjusting the concentration of solid components in the composition or the coating conditions according to the method used, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes.

[0345] Furthermore, it is also possible to apply a method of transferring a coating that has been applied and formed on a pre-support body by the above-described application method to the sealing layer.

[0346] 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.

[0347] Furthermore, a process can be performed to remove excess film from the ends of the sealing layer. Examples of such processes include edge bead rinse (EBR) and backwashing.

[0348] Alternatively, a pre-wetting process can be used: before applying the composition to the sealing layer, apply various solvents to the sealing layer to improve the wettability of the sealing layer, and then apply the composition.

[0349] <Drying Process>

[0350] After the film formation process (layer formation process), in order to remove the solvent, the above-mentioned film can be supplied to a process for drying the formed film (layer) (drying process).

[0351] That is, the rewire layer A forming process may include a drying process for drying the film formed by the film forming process.

[0352] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0353] The drying temperature of the membrane in the drying process is preferably 50°C to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Furthermore, drying can be carried out 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.

[0354] <Exposure Process>

[0355] The above-mentioned film can be used in an exposure process for selectively exposing the film.

[0356] The rewire layer A formation process may include an exposure process that selectively exposes the film formed by the film formation process.

[0357] Selective exposure refers to exposing a portion of a film. Furthermore, selective exposure creates exposed areas (exposed areas) and unexposed areas (non-exposed areas) on the film.

[0358] The exposure amount is not particularly limited as long as it is sufficient to cure the film. For example, based on the exposure energy at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ / cm. 2 More preferably 200–8,000 mJ / cm 2 .

[0359] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0360] Regarding the exposure wavelength, in terms of its relationship with 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), wide wavelengths (gamma, h, i-rays, etc.), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. In particular, exposure using high-pressure mercury lamps is preferred, and from the viewpoint of exposure sensitivity, exposure using i-rays is even more preferred.

[0361] The exposure method is not particularly limited, as long as at least a portion of the film is exposed. Examples include exposure using a photomask and exposure using laser direct imaging.

[0362] <Post-exposure heating process>

[0363] The above-mentioned film can be used in a process of heating after exposure (post-exposure heating process).

[0364] That is, the process of forming the rewire layer A may include a post-exposure heating process that heats the film exposed by the exposure process.

[0365] The post-exposure heating process can be performed after the exposure process and before the development process.

[0366] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0367] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0368] Regarding the heating rate in the post-exposure heating process, the rate from the initial heating temperature to the maximum heating temperature is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0369] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0370] The heating method used in the post-exposure heating process is not particularly limited and can use known hot plates, ovens, infrared heaters, etc.

[0371] Furthermore, during heating, it is preferable to conduct the process in a low-oxygen environment by circulating inert gases such as nitrogen, helium, or argon.

[0372] <Developing Process>

[0373] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0374] That is, the rewire layer A forming process may include a developing process that uses a developing solution to develop the film exposed by the exposure process to form a pattern.

[0375] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0376] 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.

[0377] [Developing solution]

[0378] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0379] 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 amount of 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.

[0380] 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.

[0381] Furthermore, when the developer contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferred; a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred; and a developer containing cyclopentanone is particularly preferred.

[0382] When the developer contains organic solvents, the content of organic solvents 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.

[0383] When the developer contains an organic solvent, it may also contain at least one of an alkaline compound and an alkali-generating agent. The alkaline compound and alkali-generating agent in the developer can penetrate into the pattern, sometimes improving properties such as the pattern's elongation at break.

[0384] From the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured material is further heated), organic bases are preferred as alkaline compounds.

[0385] As a basic compound, a basic compound having an amino group is preferred, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. To promote the imidization reaction, a primary amine, secondary amine, tertiary amine or ammonium salt is preferred, more preferably a secondary amine, tertiary amine or ammonium salt, further preferably a secondary amine or tertiary amine, and particularly preferably a tertiary amine.

[0386] From the viewpoint of the mechanical properties (elongation at break) of the cured product, compounds that are not easily retained in the cured film (the obtained cured product) are preferred as alkaline compounds. From the viewpoint of promoting cyclization, compounds whose residual amount is not easily reduced by vaporization or the like before heating are preferred.

[0387] Therefore, the boiling point of the alkaline compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C.

[0388] The boiling point of the alkaline compound is preferably higher than the temperature obtained by subtracting 20°C from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[0389] For example, when the boiling point of the organic solvent is 100°C, the alkaline compound used preferably has a boiling point of 80°C or higher, and more preferably a boiling point of 100°C or higher.

[0390] The developer may contain only one type of alkaline compound or two or more types of alkaline compounds.

[0391] Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, and N-methylhexylamine. N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamine ethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine, etc.

[0392] The preferred method for the alkali-generating agent is the same as that for the alkali-generating agent contained in the above composition. In particular, the alkali-generating agent is preferably a thermal alkali-generating agent.

[0393] When the developer contains at least one of an alkaline compound and an alkali-generating agent, the content of the alkaline compound or the alkali-generating agent relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the above content is not particularly limited, for example, preferably 0.1% by mass or more.

[0394] When the alkaline compound or alkali-generating agent is solid in the environment of using the developer, the content of the alkaline compound or alkali-generating agent is preferably 70 to 100% by mass relative to the total solid content of the developer.

[0395] The developer may contain only one basic compound and at least one alkali-generating agent, or it may contain two or more basic compounds and at least one alkali-generating agent. When there are two or more basic compounds and alkali-generating agents, it is preferable that their total number is within the above range.

[0396] Developer solutions may also contain other ingredients.

[0397] Other components include, for example, well-known surfactants or well-known defoamers.

[0398] [Method for supplying developer]

[0399] As long as the desired pattern can be formed, the method of supplying the developer is not particularly limited, and the following methods are available: immersing the substrate with the film formed in the developer, using a nozzle to supply the developer to the film formed on the substrate in a spin-dip development process, or a continuous supply method of the developer. The type of nozzle is not particularly limited, and examples include straight nozzles, spray nozzles, and mist nozzles.

[0400] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to supply the developer using a straight nozzle or a continuous supply method using a spray nozzle. From the viewpoint of developer penetration into the image area, it is more preferable to supply the developer using a spray nozzle.

[0401] 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.

[0402] 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.

[0403] The preferred development time is 3 seconds to 10 minutes, more preferably 5 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.

[0404] 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.

[0405] [Rinse solution]

[0406] 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.

[0407] When the rinsing solution contains an organic solvent, examples of organic solvents that are the same as those exemplified when the developing solution contains an organic solvent can be given.

[0408] The organic solvent contained in the rinsing solution is preferably an organic solvent that is different from the organic solvent contained in the developing solution, and more preferably an organic solvent that has a lower solubility in the pattern compared to the organic solvent contained in the developing solution.

[0409] When the rinsing solution contains organic solvents, one or more organic solvents may be used, or a mixture of two or more may be used. Preferred organic solvents include cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME; more preferably, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME; and even more preferably, cyclohexanone and PGMEA.

[0410] 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.

[0411] The rinsing solution may contain at least one of an alkaline compound and an alkali-generating agent.

[0412] While not particularly limited, when the developer contains an organic solvent, the rinsing solution containing at least one of an organic solvent, an alkaline compound, and an alkali-generating agent is also a preferred embodiment of the present invention.

[0413] Examples of alkaline compounds and alkali-generating agents contained in the rinsing solution include alkaline compounds that may be contained in the developer solution when it contains organic solvents, and examples of compounds that serve as alkali-generating agents. The preferred methods are also the same.

[0414] Regarding the alkaline compounds and alkali-generating agents contained in the rinsing solution, their solubility in the solvent of the rinsing solution can be considered when selecting them.

[0415] When the rinsing solution contains at least one of an alkaline compound and an alkali-generating agent, the content of the alkaline compound or the alkali-generating agent relative to the total mass of the rinsing solution is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the above content is not particularly limited, for example, preferably 0.1% by mass or more.

[0416] When the alkaline compound or alkali-generating agent is solid in the environment of using the rinsing solution, the content of the alkaline compound or alkali-generating agent is preferably 70 to 100% by mass relative to the total solid content of the rinsing solution.

[0417] When the rinsing solution contains at least one of an alkaline compound and an alkali-generating agent, the rinsing solution may contain only one type of alkaline compound and alkali-generating agent, or it may contain at least two or more types of alkaline compounds and alkali-generating agents. When there are two or more types of alkaline compounds and alkali-generating agents, it is preferable that their total number falls within the above-mentioned range.

[0418] The rinsing solution may also contain other ingredients.

[0419] Other components include, for example, well-known surfactants or well-known defoamers.

[0420] [Method for supplying flushing fluid]

[0421] As long as the desired pattern can be formed, the method of supplying the rinsing liquid is not particularly limited, and the following methods are available: immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by liquid accumulation, supplying the rinsing liquid to the substrate by spraying, and continuously supplying the rinsing liquid to the substrate by means of a straight nozzle.

[0422] From the viewpoints of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, there are methods for supplying rinsing fluid using spray nozzles, straight nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred, and from the viewpoint of the penetrability of the rinsing fluid to the image area, a mist nozzle supply method is even more preferred. The type of nozzle is not particularly limited; examples include straight nozzles, spray nozzles, and mist nozzles.

[0423] 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.

[0424] As a method for supplying rinsing fluid in the rinsing process, methods such as continuously supplying rinsing fluid to the substrate, maintaining the rinsing fluid on the substrate in a substantially static state, vibrating the rinsing fluid on the substrate using ultrasound or the like, and combining these methods are all possible.

[0425] 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°C ​​to 30°C.

[0426] In the developing process, after treatment with developer or cleaning of the pattern with rinsing solution, a step may be included to bring the treatment solution into contact with the pattern. Furthermore, methods may be employed such as supplying the treatment solution before the developer or rinsing solution in contact with the pattern has completely dried.

[0427] Examples of treatment solutions include those containing at least one of water and an organic solvent, and at least one of an alkaline compound and an alkali-generating agent.

[0428] The preferred methods for at least one of the above-mentioned organic solvents, basic compounds, and alkali-generating agents are the same as the preferred methods for the organic solvents, basic compounds, and alkali-generating agents used in the above-mentioned rinsing solutions.

[0429] The method of supplying the processing liquid to the pattern can be the same as the method of supplying the rinsing liquid described above, and the preferred method is also the same.

[0430] The content of alkaline compounds or alkali-generating agents in the treatment solution is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment solution. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example.

[0431] Furthermore, when the alkaline compound or alkali-generating agent is solid in the environment of the treatment liquid, the content of the alkaline compound or alkali-generating agent is preferably 70 to 100% by mass relative to the total solid content of the treatment liquid.

[0432] When the treatment solution contains at least one of an alkaline compound and an alkali-generating agent, the treatment solution may contain only one type of alkaline compound and alkali-generating agent, or it may contain at least two or more types of alkaline compounds and alkali-generating agents. When there are two or more types of alkaline compounds and alkali-generating agents, it is preferable that their total number falls within the above-mentioned range.

[0433] <Heating Process>

[0434] The pattern obtained by the developing process (or the washed pattern if a washing process is performed) can be used in a heating process for heating the pattern obtained by the developing process described above.

[0435] That is, the process of forming the rewire layer A may include a heating process that heats the pattern obtained by the developing process.

[0436] During the heating process, resins such as polyimide precursors are cyclized to become resins such as polyimide.

[0437] Furthermore, crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed.

[0438] The heating temperature (maximum heating temperature) in the heating process is preferably 50-450°C, more preferably 150-350°C, even more preferably 150-250°C, even more preferably 160-250°C, and particularly preferably 160-230°C.

[0439] 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-producing agent.

[0440] Regarding the heating process, it is preferable to raise the temperature from the initial temperature to the maximum heating temperature at a rate of 1 to 12°C / minute. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. Setting the heating rate to 1°C / minute or higher ensures productivity and prevents excessive evaporation of acid or solvent, while setting the heating rate to 12°C / minute or lower helps to mitigate residual stress in the cured product.

[0441] Furthermore, in the case of an oven capable of rapid heating, it is preferable to raise the temperature from the initial temperature to the maximum heating temperature at a heating rate of 1 to 8°C / second, more preferably at a heating rate of 2 to 7°C / second, and even more preferably at a heating rate of 3 to 6°C / second.

[0442] 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, in the case of drying the composition after application to a substrate, it is the temperature of the dried film (layer), preferably starting at a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the composition.

[0443] 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.

[0444] 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.

[0445] 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.

[0446] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / min and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C / min and holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is also 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 of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment process can be a two-stage or more process; for example, the first stage of the pretreatment process can be performed in the range of 100–150°C, and then the second stage of the pretreatment process can be performed in the range of 150–200°C.

[0447] Furthermore, cooling can be performed after heating, and the preferred cooling rate at this time is 1 to 5°C / minute.

[0448] Regarding the heating process, from the viewpoint of preventing the decomposition of specific resins, it is preferable to carry out the process in a low-oxygen environment by passing inert gases such as nitrogen, helium, or argon under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0449] As a heating method in the heating process, it is not particularly limited, and examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0450] <Post-development exposure process>

[0451] The pattern obtained through the developing process (or the washed pattern in the case of a washing process) can also replace the heating process described above, or, in addition to the heating process described above, be used in a post-developing exposure process to expose the pattern after the developing process.

[0452] That is, the process of forming re-line layer A may include a post-development exposure process that exposes the pattern obtained by the development process. The process of forming re-line layer A may include a heating process and a post-development exposure process, or it may include only one of the heating process and the post-development exposure process.

[0453] In the post-development exposure process, for example, it can promote the cyclization reaction of polyimide precursors, etc., by photosensitive alkali-generating agents, and the departure reaction of acid-decomposing groups by photosensitive acid-generating agents.

[0454] In the post-development exposure process, it is sufficient for at least a portion of the pattern obtained in the development process to be exposed, but it is preferable for all of the pattern to be exposed.

[0455] 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 .

[0456] Regarding the post-development exposure process, for example, the light source used in the above-mentioned exposure process can be used, preferably broadband light.

[0457] <Metal Layer Formation Process>

[0458] 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.

[0459] The pattern obtained by the developing process corresponds to the insulating pattern A, and the metal layer formed by the metal layer forming process corresponds to the conductive pattern A.

[0460] That is, the rewire layer A forming process preferably includes a metal layer forming process that forms a metal layer on a pattern obtained by the developing process (preferably a pattern for at least one of the heating process and the post-developing exposure process).

[0461] As a metal layer, it is not particularly limited and can use existing metal types, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0462] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, 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 or copper cyanide plating solutions can be cited.

[0463] Furthermore, the metal layer formation process preferably includes forming a barrier layer on the formed metal layer after the metal layer has been formed. Conventionally known methods can be used as the method for forming the barrier layer without particular limitation.

[0464] 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.

[0465] <Resist layer formation process, resist layer stripping process>

[0466] Here, the process of forming the rewiring layer A can include a process of forming a resist layer before the process of forming the metal layer.

[0467] Furthermore, the process of forming the rewiring layer A can include a resist layer stripping process after the metal layer formation process.

[0468] These processes can be carried out using known methods.

[0469] By performing these processes, it is also possible to form lines and spatial patterns as conductive patterns A.

[0470] <Grinding Process>

[0471] The process of forming the rewiring layer A may also include a grinding process that grinds the surface of the rewiring layer A after the metal layer formation process.

[0472] Examples of grinding methods include chemical mechanical polishing (CMP) and physical polishing, but are not limited to these; known methods can be used without particular restriction.

[0473] <Layering Process>

[0474] The rewiring layer A forming process of the present invention preferably includes a lamination process.

[0475] 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 process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. This can be achieved by repeating at least one of (a) film formation process, (d) heating process, and post-development exposure process. Furthermore, (e) metal layer formation process can be included after at least one of (d) heating process and post-development exposure process. The lamination process may also appropriately include the aforementioned drying process, etc.

[0476] When a further lamination process is performed after the lamination process, a surface activation treatment process can be performed after the aforementioned exposure process, and after the aforementioned heating process or after the aforementioned metal layer formation process. Plasma treatment is exemplified as a surface activation treatment. Details regarding surface activation treatment will be described later.

[0477] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0478] For example, a structure of resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferred, with the resin layer having 2 or more layers and 20 or fewer layers, and more preferably 2 or more layers and 9 or fewer layers.

[0479] The composition, shape, and film thickness of the above layers can be the same or different.

[0480] In the process of forming the rewiring layer A, it is particularly preferable to further form a cured product (resin layer) of the above composition to cover the metal layer after the metal layer is formed. Specifically, examples include repeating at least one of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating at least one of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination process of the composite composition layer (resin layer) and the metal layer formation process, the composite composition layer (resin layer) and the metal layer can be alternately laminated.

[0481] <Surface activation treatment process>

[0482] The process of forming the rewiring layer A preferably includes a surface activation process that performs surface activation treatment on at least a portion of the metal layer and the composition layer.

[0483] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the development process (preferably after at least one of the heating process and the post-development exposure process) or after the surface activation treatment process of the composition layer.

[0484] Surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed composition layer, or on at least a portion of both the metal layer and the exposed composition layer. Preferably, surface activation treatment is performed on at least a portion of the metal layer, and more preferably on a portion or all of the region of the metal layer where the composition layer is formed on the surface. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the composition layer (film) disposed on its surface can be improved.

[0485] Surface activation treatment is preferably performed on part or all of the exposed composition layer (resin layer). In this way, by performing surface activation treatment on the surface of the composition layer, the adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. In particular, when the composition layer is cured, such as during negative development, it is less likely to be damaged by the surface treatment, thereby easily improving adhesion.

[0486] 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.

[0487] <Connector Pad Forming Process>

[0488] The process of forming the rewiring layer A may include a process of forming a connection pad after the lamination process. The preferred configuration of the formed connection pad is as described above.

[0489] The bonding pad forming process can use methods known in the art without particular restriction. For example, a method can be described as forming a bonding pad by plating after forming a resist layer as needed, and then peeling off the resist layer.

[0490] Here, the above-mentioned rewiring layer A forming process includes a step of coating the above-mentioned insulating pattern A forming composition onto the sealing layer to form a coating film, a step of drying, exposing and developing the above-mentioned coating film to form a precursor pattern A, and a step of heating the above-mentioned precursor pattern A to obtain the insulating pattern A. Furthermore, the method in which the film thickness variation rate of the above-mentioned insulating pattern A relative to the above-mentioned precursor pattern A is less than 20% is also one of the preferred embodiments of the present invention.

[0491] Here, the above-mentioned coating, drying, exposure, development and heating are carried out through the above-mentioned film forming process, drying process, exposure process, development process and heating process.

[0492] The above film thickness change rate is calculated as (film thickness of precursor pattern A - film thickness of insulating pattern A) / film thickness of precursor pattern A × 100.

[0493] The aforementioned film thickness variation rate is preferably 15% or less, more preferably 10% or less. Furthermore, the lower limit of the aforementioned film thickness variation rate is not particularly limited, and 0% or more is acceptable.

[0494] <Re-wiring layer B formation process>

[0495] The method for manufacturing the laminate of the present invention includes a rewiring layer B forming step, wherein the rewiring layer B forming step forms a rewiring layer B comprising an insulating pattern B and a conductive pattern B existing between the patterns of the insulating pattern B on the surface of the sealing layer that does not expose the circuit.

[0496] The rewiring layer B is formed on the surface of the sealing material that does not expose the circuit described above through the rewiring layer B forming process. The preferred embodiment of the rewiring layer B is the same as the preferred embodiment of the rewiring layer B in the laminate of the present invention described above.

[0497] In the process of forming the rewiring layer B, except that it is formed on the surface of the sealing material where the circuit is not exposed, it can be carried out by the same method as the process of forming the rewiring layer A.

[0498] In the process of forming the rewiring layer B, the composition for forming the insulating pattern A can also be used to form the rewiring layer B in the same manner as the formation of the rewiring layer A.

[0499] Here, the composition for forming the insulating pattern A used to form the redistribution layer A and the composition for forming the insulating pattern A used to form the redistribution layer B may have the same or different compositions.

[0500] Furthermore, either the rewiring layer B formation process or the rewiring layer A formation process can be performed first.

[0501] <Carrier wafer bonding process, carrier wafer peeling process>

[0502] The manufacturing method of the laminate of the present invention can include: a carrier wafer bonding step of bonding a carrier wafer to the laminate being manufactured, and a carrier wafer peeling step of peeling off the bonded carrier wafer.

[0503] For example, in the process of forming a sealing layer, a carrier wafer is bonded to a component with circuitry to form a sealing layer, and a rewiring layer A is formed on the sealing layer through a rewiring layer A forming process. In order to form a rewiring layer B, the carrier wafer is peeled off from the sealing layer, and a new carrier wafer is bonded to the surface of the rewiring layer A as needed. This also allows the surface of the carrier wafer to be reversed.

[0504] The carrier wafer peeling process and the carrier wafer bonding process can be carried out by known methods.

[0505] Furthermore, known carrier chips can be used without special restrictions as carrier chips.

[0506] <Conductive component forming process>

[0507] The manufacturing method of the laminate of the present invention may further include a conductive portion forming step for forming the above-mentioned conductive portion.

[0508] The conductive part forming process can be performed, for example, between the sealing layer forming process and the rewiring layer A forming process and the rewiring layer B forming process, or after at least one of the rewiring layer A forming process and the rewiring layer B forming process.

[0509] The conductive part forming process is performed, for example, by forming a hole in the sealing layer using a laser or the like, and filling the hole with a conductor by plating or the like.

[0510] The holes mentioned above can be through holes or non-through holes.

[0511] Furthermore, in the formation of the aforementioned holes, residues such as the sealing layer generated during processing can be removed by known desmearing treatments.

[0512] As a method for forming conductive parts, methods known in the art can be used without particular restriction.

[0513] <Inspection Procedure>

[0514] After at least one of the rewiring layer A formation process and the rewiring layer B formation process, an inspection process may be included to check the surface shape, conductivity, insulation, presence or absence of voids of at least one of the formed rewiring layer A and rewiring layer B.

[0515] As a method for inspection procedures, methods known in the art can be used without particular restriction.

[0516] <Forming process of connecting component A>

[0517] The manufacturing method of the laminate of the present invention may further include a step of forming a connecting member A on the surface of the above-mentioned rewiring layer A that is different from the surface that contacts the above-mentioned sealing layer.

[0518] The preferred embodiment of connecting component A is the same as the preferred embodiment of connecting component A in the laminate of the present invention.

[0519] As a method for forming the connecting component A, methods known in the art can be used without particular restriction.

[0520] <Other Functional Grain Bonding Processes>

[0521] The manufacturing method of the laminate of the present invention may further include a step of bonding other functional grains to the surfaces of the above-mentioned rewiring layer A that are different from the surfaces that contact the above-mentioned sealing layer.

[0522] Other functional grains are preferably connected to the redistribution layer A via the aforementioned connecting component A.

[0523] The preferred configurations for other functional grains are the same as those for other functional grains in the laminate of the present invention.

[0524] When bonding other functional grains, at least one of heating and pressurization can be performed. As a method for bonding other functional grains, methods known in the art can be used without particular limitation.

[0525] In the manufacturing method of the laminate of the present invention, the component having the above-mentioned circuit is a wiring layer, and the process of bonding the above-mentioned rewiring layer A with two or more other functional grains is also one of the preferred embodiments of the present invention.

[0526] The bonding of two or more other functional grains can be performed separately through the aforementioned bonding process for other functional grains. These can be bonded simultaneously or separately.

[0527] <Connecting Component B Forming Process>

[0528] The manufacturing method of the laminate of the present invention may further include a step of forming a connecting member B on the surface of the above-mentioned rewiring layer B that is different from the surface that contacts the above-mentioned sealing layer.

[0529] The preferred embodiment of connecting component B is the same as the preferred embodiment of connecting component B of the laminate of the present invention.

[0530] As a method for forming the connecting component B, methods known in the art can be used without particular restriction.

[0531] <Circuit component bonding process>

[0532] The manufacturing method of the laminate of the present invention may further include a step of bonding circuit components to the surfaces of the above-mentioned rewiring layer B and the surfaces that contact the above-mentioned sealing layer.

[0533] The circuit components are preferably connected to the redistribution layer B via the aforementioned connection component B.

[0534] The preferred embodiment of the circuit components is the same as that of the circuit components of the laminate of the present invention.

[0535] When joining circuit components, at least one of heating and pressurization can be performed. As a method for joining circuit components, methods known in the art can be used without particular limitation.

[0536] <Other Processes>

[0537] The manufacturing method of the laminate of the present invention may also include other steps.

[0538] Other processes include cleaning components as needed after each process.

[0539] <Specific Examples of Manufacturing Methods for Laminated Materials>

[0540] Hereinafter, examples of specific methods for manufacturing the laminate of the present invention will be shown in the figures for illustration, but the present invention is not limited to these examples.

[0541] In some figures, symbols that have already been explained are omitted.

[0542] Figure 5 This is a schematic cross-sectional view illustrating an example of a method for manufacturing a laminate according to the present invention.

[0543] Figure 5 (a) is a schematic cross-sectional view showing the state in which the component 18 with circuitry is bonded to the carrier wafer 62.

[0544] exist Figure 5 Although the description is omitted in (a), a pre-adhesive layer may be formed on the component 18 side of the circuit having the carrier wafer 62.

[0545] The component 18 having circuitry includes a semiconductor component 22 and a circuit 20, with the circuit 20 sandwiching the semiconductor component 22 and disposed on the side opposite to the carrier wafer 62. The component 18 having circuitry is described as a functional die including the semiconductor component 22, but when the component 18 having circuitry is a wiring layer, the component 18 having circuitry may consist only of the circuit 20, or the semiconductor component 22 may not be present.

[0546] Figure 5(b) is a schematic cross-sectional view showing the state in which a sealing layer 12, including a component 18 having circuitry and a sealing material 24, is formed on a carrier wafer 62 through a sealing layer forming process.

[0547] By applying the cured composition Figure 5 (a) The sealing layer 12 is obtained by forming a sealing material from the carrier wafer 62 and the component 18 having circuits shown, and by curing them.

[0548] Before proceeding with the subsequent rewiring layer A formation process, the surface of the sealing layer 12 can be ground to expose the circuit 20 by the above method, or the passivation layer formation process can be performed on the surface having the circuit 20.

[0549] Figure 5 (c) is a schematic cross-sectional view showing the state after the second carrier wafer 64 is bonded and the carrier wafer 62 is peeled off after the rewiring layer A14 is formed by the rewiring layer A forming process.

[0550] right Figure 5 The rewiring layer A is formed by performing a rewiring layer A process on the surface of the sealing layer 12 with circuit 20 as described in (b).

[0551] Here, after the rewiring layer A formation process, a second carrier wafer 64, which is different from the carrier wafer 62, is bonded to the rewiring layer A, and the carrier wafer 62 is peeled off, thereby exposing the side of the sealing layer 12 that is different from the side on which the rewiring layer A is formed (reversal process).

[0552] Figure 5 (d) is a schematic cross-sectional view showing the state in which a conductive through-hole 26 is formed by a conductive part forming process and a redistribution layer B16 is formed by a redistribution layer B forming process.

[0553] right Figure 5 (c) describes a process for forming a conductive part in the sealing material 24 of the sealing layer 12, thereby forming a conductive through hole 26.

[0554] Furthermore, regarding Figure 5 The rewiring layer B is formed by performing a rewiring layer B process on the side of the sealing layer 12 that does not have the circuit 20 as described in (c).

[0555] Subsequently, the laminate of the present invention is obtained by peeling off the second carrier wafer 64.

[0556] Figure 6 This indicates that other functional grains will be further bonded to... Figure 5 (d) is a schematic cross-sectional view of an example of a stacked structure.

[0557] exist Figure 6In the middle, the third carrier chip 66 is bonded to Figure 5 (d) shows the rewiring layer B16 in the stack and the second carrier wafer 64 is stripped.

[0558] After stripping the second carrier wafer 64, a connection component A formation process is performed. After forming the connection component A28 on the redistribution layer A14, a further functional die bonding process is performed, bonding two other functional dies 32, thereby obtaining... Figure 6 The layered structure shown.

[0559] Here, underfill material can be further filled between the redistribution layer A14 and other functional grains 32.

[0560] Subsequently, the stacked assembly from which the third carrier wafer 66 has been stripped can be used as a semiconductor package.

[0561] Figure 7 This indicates that the circuit components will be further joined to Figure 6 A schematic cross-sectional view of an example of a stacked structure.

[0562] exist Figure 7 middle, Figure 6 The third carrier wafer 66 in the stack shown is peeled off.

[0563] After stripping the third carrier wafer 66, a connection component B forming process is performed, and a connection component B30 is formed in the redistribution layer B16 and a circuit component bonding process is performed to bond the circuit component 34, thereby obtaining a laminate.

[0564] The following is a detailed description of the composition (composition) for forming insulating pattern A.

[0565] As a composition, known compositions for forming insulating patterns can be used without particular limitation, but preferably contain at least one resin selected from the group consisting of heterocyclic polymers and their precursors (hereinafter also referred to as "specific resins"), more preferably containing polyimide or polyimide precursor.

[0566] The imidization rate of the above-mentioned polyimide precursor is preferably less than 50%.

[0567] The imidization rate of the above-mentioned polyimide is preferably 50% or higher.

[0568] Details regarding the imidization rate will be discussed later.

[0569] <Specific Resins>

[0570] The heterocyclic polymer is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

[0571] In this invention, "main chain" refers to the longest bonded chain in the resin molecule, and "side chain" refers to the bonded chain other than the main chain.

[0572] Examples of heterocyclic polymers include polyimide, polybenzoxazole, and polyamide-imide.

[0573] The precursor of a heterocyclic polymer refers to a resin that becomes a heterocyclic polymer by undergoing a change in its chemical structure through external stimulation. Preferably, it is a resin that becomes a heterocyclic polymer by undergoing a change in its chemical structure through heat. More preferably, it is a resin that becomes a heterocyclic polymer by forming a ring structure through a ring-closing reaction through heat.

[0574] Examples of precursors for heterocyclic polymers include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

[0575] That is, the composition preferably contains at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide imide and polyamide imide precursor as a specific resin.

[0576] The composition preferably contains polyimide or a polyimide precursor as a specific resin.

[0577] Furthermore, the specific resin is preferably a resin having at least one repeating unit selected from the group consisting of repeating units represented by formula (2) and repeating units represented by formula (4) described later.

[0578] The resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0579] When a particular resin has free radical polymerizable groups, the composition preferably contains a free radical polymerization initiator, more preferably a free radical polymerization initiator and a free radical crosslinking agent. Furthermore, a sensitizer may be included, if desired. Such a composition can, for example, form a negative photosensitive film.

[0580] Furthermore, certain resins may have polar conversion groups such as acid-decomposing groups.

[0581] When a particular resin has acid-degrading groups, the composition preferably contains a photoacid-generating agent. Such a composition can, for example, form a chemically amplified positive or negative photosensitive film.

[0582] [Polyimide precursor]

[0583] The type of polyimide precursor used in this invention is not particularly limited, but preferably contains repeating units represented by the following formula (2).

[0584] [Chemical Formula 3]

[0585]

[0586] In equation (2), A 1 and A 2 Each 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 Each can independently represent a hydrogen atom or a monovalent organic group, R z It represents a hydrogen atom or a monovalent organic group.

[0587] A in equation (2) 1 and A 2 Each independently represents an oxygen atom or -NR. z - Preferably, it contains oxygen atoms.

[0588] R z It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0589] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups containing aromatic groups with 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the hydrocarbon groups in the ring members of the aforementioned cyclic aliphatic groups and aromatic groups can be replaced by groups containing heteroatoms. R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, with a preference for groups represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Their preferred ranges are as described above.

[0590] R 111 The preferred diamine is derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0591] Specifically, R 111The preferred diamine is a diamine containing a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof; more preferably, a diamine containing an aromatic group with 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the hydrocarbon groups of the ring members of the aforementioned cyclic aliphatic groups and aromatic groups can be replaced by groups containing heteroatoms. Examples of groups containing aromatic groups include the following groups.

[0592] [Chemical Formula 4]

[0593]

[0594] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0595] In the formula, * indicates the bonding site with other structures.

[0596] As diamines, examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane.

[0597] 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine;

[0598] m-Phenylenediamine or p-Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2, 2-Bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(2-aminophenoxy)phenyl] sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4' -Dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, At least one diamine selected from the following: 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, or 4,4'-diaminotetraphenyl.

[0599] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0600] Furthermore, the diamine having two or more alkylene glycol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may also be preferred.

[0601] From the perspective of the flexibility of the obtained organic membrane, R 111 Preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0602] Furthermore, from the perspective of i-ray transmittance, R 111 Preferably, it is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0603] Equation (51)

[0604] [Chemical Formula 5]

[0605]

[0606] In equation (51), R 50 ~R 57 Each can be independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * represents the bonding site with the nitrogen atom in formula (2) independently.

[0607] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0608] [Chemical Formula 6]

[0609]

[0610] In equation (61), R 58 and R 59 Each of the above can be independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * can be independently represented by the bonding site with the nitrogen atom in formula (2).

[0611] Examples of diamines that impart the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used.

[0612] Furthermore, R 111 It is also preferable to use a group represented by the following formula (71). In the above manner, R 111 More preferably, it is a group represented by the following formula (72).

[0613] [Chemical Formula 7]

[0614]

[0615] In equation (71), A 1 ~A 3 Each is a single bond or a divalent linker, and * indicates the bonding site with the nitrogen atom in formula (2). The hydrogen atoms of the four benzene rings recorded in formula (71) can be replaced by substituents.

[0616] In this specification, a bond that intersects the edge of a ring structure refers to a bond that replaces any one of the hydrogen atoms in the ring structure.

[0617] In equation (72), * represents the bonding site with the nitrogen atom in equation (2).

[0618] In equation (71), A 1 ~A 3 Preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a combination of two or more thereof. More preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, or a combination of two or more thereof. Even more preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms or -O- that can be replaced by a fluorine atom.

[0619] In particular, A 1 and A 3 The preferred option is -O-.

[0620] In particular, A 2 Preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by fluorine atoms.

[0621] Among these, A 1 and A 3 For -O- and A 2 The -C(CH3)2- configuration is also one of the preferred embodiments of the present invention.

[0622] The number of carbon atoms in the aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by fluorine atoms is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.

[0623] Specific examples of aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms include -CH2-, -C(CH3)2-, and -C(CF3)2-, among which -C(CH3)2- is preferred.

[0624] Examples of substituents in the four benzene rings described in formula (71) include fluorine atoms, hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms.

[0625] Furthermore, the fact that all four benzene rings described in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.

[0626] Furthermore, R 111 It is also preferable to use a group represented by the following formula (81). In the above manner, R 111 More preferably, it is a group represented by the following formula (82).

[0627] [Chemical Formula 8]

[0628]

[0629] In equation (81), A 1 and A 2 Each is a single bond or a divalent linker, and * indicates the bonding site with the nitrogen atom in formula (2). The hydrogen atoms in the three benzene rings recorded in formula (81) can be replaced by substituents.

[0630] In equation (82), * represents the bonding site with the nitrogen atom in equation (2).

[0631] In equation (81), A 1 and A 2 Each group is preferably an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a combination of two or more thereof. More preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, or a combination of two or more thereof. Even more preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom or -O-. Particularly preferred is -C(CH3)2-.

[0632] R in equation (2) 115 It represents a tetravalent organic group. As a tetravalent organic group, it is preferred to be a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

[0633] In equation (5) or equation (6), * independently represents the bonding site with other structures.

[0634] [Chemical Formula 9]

[0635]

[0636] In equation (5), R 112 It is a single bond or a divalent linker, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0637] Furthermore, R 115 It is also preferable to use a group represented by the following formula (7). In the above manner, R 115More preferably, it is a group represented by the following formula (7-2).

[0638] [Chemical Formula 10]

[0639]

[0640] In equation (7), A 1 ~A 3 Each is a single bond or a divalent linker, and * indicates the bonding site with the carbonyl group in formula (2). The hydrogen atoms of the four benzene rings recorded in formula (7) can be replaced by substituents.

[0641] In equation (7-2), * indicates the bonding site with the carbonyl group in equation (2).

[0642] In equation (7), A 1 ~A 3 The preferred method for the substituents in the benzene ring is the same as that for A in formula (7-1) above. 1 ~A 3 The preferred method is the same as that for substituents in the benzene ring.

[0643] Specifically, R 115 Examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. As a counterpart to R... 115 The structure of the polyimide precursor can contain only one tetracarboxylic dianhydride residue or more than two tetracarboxylic dianhydride residues.

[0644] Tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0645] [Chemical Formula 11]

[0646]

[0647] In equation (O), R 115 This indicates a tetravalent organic group. R 115 The meaning of R in equation (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0648] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0649] Furthermore, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can be cited as preferred examples.

[0650] In equation (2), R can also be used. 111 and R 115 At least one of them has an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0651] R in equation (2) 113 and R 114 Each can be independently represented by a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferred to contain a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxide group. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction through the action of heat, free radicals, etc., and is preferably a free radical polymerizable group. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. As for the free radical polymerizable group in the polyimide precursor, a group having an olefinic unsaturated bond is preferred.

[0652] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, and preferably groups represented by formula (III) below.

[0653] [Chemical Formula 12]

[0654]

[0655] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0656] In equation (III), * indicates the bonding site with other structures.

[0657] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0658] R 201 Preferred examples include alkylene compounds such as ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, and polyalkoxide compounds; more preferably, alkylene compounds such as ethylene and propyleneene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds; and even more preferably, alkylene compounds such as ethylene and propyleneene or polyalkoxide compounds.

[0659] In this invention, polyalkoxide refers to a group consisting of two or more alkoxide groups directly bonded together. The alkylene groups within the multiple alkoxide groups in a polyalkoxide group may be the same or different.

[0660] When polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0661] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

[0662] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0663] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0664] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or groups bonded to multiple ethoxy groups and multiple propoxy groups are preferred as polyvinyloxy groups, more preferably polyvinyloxy or polypropyleneoxy, and even more preferably polyvinyloxy. Among the aforementioned groups bonded to multiple ethoxy and propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, form blocks, or be arranged in alternating patterns. The preferred manner for the number of repetitions of the ethoxy groups, etc., is as described above.

[0665] In equation (2), when R 113 When it is a hydrogen atom or R 114 When the hydrogen atom is present, the polyimide precursor can form a salt pair with a tertiary amine compound having an olefinically unsaturated bond. N,N-dimethylaminopropyl methacrylate is an example of such a tertiary amine compound having an olefinically unsaturated bond.

[0666] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes through the action of acid to produce a base-soluble group such as a phenolic hydroxyl group or a carboxyl group. It is preferred to have an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.

[0667] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0668] The polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0669] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0670] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in this invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the range of exposure latitude can be further increased.

[0671] Equation (2-A)

[0672] [Chemical Formula 13]

[0673]

[0674] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, preferably both of them are groups containing polymerizable groups.

[0675] A 1 A 2 R 111 R 113 and R 114 The meanings are independently related to A in equation (2). 1 A 2 R 111 R 113 and R 114 The meanings are the same, and the preferred ranges are also the same. R 112 The meaning of R in equation (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0676] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units represented by formula (2). Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit represented by formula (2) above, the polyimide precursor may also contain other types of repeating units.

[0677] As one embodiment of the polyimide precursor in this invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide except for the end units can be repeating units represented by formula (2).

[0678] - Cyclization rate (imideization rate) -

[0679] From the viewpoint of the obtained organic membrane's strength and insulation properties, the cyclization rate (imidization rate) of the polyimide precursor is preferably less than 50%, more preferably less than 40%, further preferably less than 30%, and even more preferably less than 20%.

[0680] The lower limit of the cyclization rate mentioned above is not specifically limited; 0% is sufficient.

[0681] The cyclization rate described above can be determined, for example, by the following method.

[0682] The infrared absorption spectrum of the polyimide precursor was measured, and the absorption peak at 1377 cm⁻¹, which is derived from the imide structure, was determined. -1 The peak intensity P1 is located nearby. Next, after heat-treating the polyimide precursor at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P1 at 1377 cm⁻¹ was determined. -1 The peak intensity P2 is nearby. Using the obtained peak intensities P1 and P2, the cyclization rate of the polyimide precursor can be calculated according to the following formula.

[0683] Cycloning rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0684] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. 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.

[0685] 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. The upper limit of the molecular weight dispersion of the polyimide precursor is not specifically defined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0686] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0687] When the 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.

[0688] [Polyimide]

[0689] The polyimide used in this invention can be an alkali-soluble polyimide or a polyimide soluble in a developer solution with organic solvent as the main component.

[0690] In this specification, alkali-soluble polyimide refers to polyimide in which 0.1 g or more is dissolved in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferable to dissolve 0.5 g or more of polyimide, and more preferably 1.0 g or more of polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but it is preferably 100 g or less.

[0691] From the viewpoint of the strength and insulation of the obtained organic membrane, polyimide is preferably a polyimide having multiple imide structures on the main chain.

[0692] -Fluorine atom-

[0693] From the viewpoint of the membrane strength of the obtained organic membrane, polyimide is also preferably provided with fluorine atoms.

[0694] Fluorine atoms are preferably included, for example, in the repeating unit represented by equation (4) described later. 132 Or, as will be discussed later, R in the repeating unit represented by equation (4). 131 More preferably, R is included in the repeating unit represented by equation (4) described later. 132 Or, as will be discussed later, R in the repeating unit represented by equation (4). 131 It is used as a fluorinated alkyl group.

[0695] The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0696] -Silicon atom-

[0697] From the viewpoint of the strength of the obtained organic membrane, polyimide is also preferably composed of silicon atoms.

[0698] Silicon atoms are preferably included, for example, in the repeating unit represented by equation (4) described later. 131 More preferably, R is included in the repeating unit represented by equation (4) described later. 131 The structure is referred to later as an organically modified (poly)siloxane.

[0699] The aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structure may also be included in the side chain of the polyimide, but preferably in the main chain of the polyimide.

[0700] The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0701] -ene unsaturated bond-

[0702] From the viewpoint of the strength of the obtained organic membrane, polyimide preferably has olefinic unsaturated bonds.

[0703] Polyimide can have olefinic unsaturated bonds at the end of the main chain or on the side chain, but it is preferred to have olefinic unsaturated bonds on the side chain.

[0704] The aforementioned olefinic unsaturated bonds preferably possess free radical polymerization properties.

[0705] The olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 132 Or R 131 More preferably, it is included in R 132 Or R 131 It is a group with an olefinic unsaturated bond.

[0706] In these, the olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 131 More preferably, it is included in R 131 It is a group with an olefinic unsaturated bond.

[0707] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, and other vinyl groups that are directly bonded to the aromatic ring and can be substituted, as well as (meth)acrylamido, (meth)acryloyloxy, and groups represented by the following formula (IV).

[0708] [Chemical Formula 14]

[0709]

[0710] In equation (IV), R 20 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0711] In equation (IV), R 21 It refers to an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkoxide group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3. The number of repetitions of the alkoxide group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3) or a group formed by combining two or more of these.

[0712] As the aforementioned alkylene groups having 2 to 12 carbon atoms, they can be any of the following: linear, branched, cyclic, or a combination thereof.

[0713] As the aforementioned alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0714] Among these, R 21 Preferably, it is a group represented by any one of the following formulas (R1) to (R3), and more preferably, it is a group represented by formula (R1).

[0715] [Chemical Formula 15]

[0716]

[0717] In formulas (R1) to (R3), L represents a single bond or an alkylene group with 2 to 12 carbon atoms, a (poly)alkoxide group with 2 to 30 carbon atoms, or a group formed by bonding two or more of them; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a group with R in formula (IV). 21 The bonding sites of the bonded oxygen atoms.

[0718] In formulas (R1) to (R3), the preferred form of L is an alkylene group having 2 to 12 carbon atoms or a (poly)alkene group having 2 to 30 carbon atoms, and is also R in formula (IV). 21 The preferred configurations are the same for alkylene groups with 2 to 12 carbon atoms or (poly)alkoxide groups with 2 to 30 carbon atoms.

[0719] In formula (R1), X is preferably an oxygen atom.

[0720] In equations (R1) to (R3), the meaning of * is the same as that of * in equation (IV), and the preferred method is also the same.

[0721] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having hydroxyl groups such as phenolic hydroxyl groups with a compound having isocyanate groups and olefinic unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate).

[0722] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having hydroxyl and olefinic unsaturated bonds (e.g., 2-hydroxyethyl methacrylate, etc.).

[0723] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having hydroxyl groups such as phenolic hydroxyl groups with a compound having glycidyl groups and olefinic unsaturated bonds (e.g., glycidyl methacrylate, etc.).

[0724] In formula (IV), * represents the bonding site with other structures, and * is preferably the bonding site with the main chain of polyimide.

[0725] The amount of olefinic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0726] - Polymerizable groups other than those with olefinic unsaturated bonds-

[0727] Polyimides can have polymerizable groups other than those with olefinic unsaturated bonds.

[0728] Examples of polymerizable groups other than those with olefinic unsaturated bonds include cyclic ether groups such as epoxy and oxobutyl groups, alkoxymethyl groups such as methoxymethyl, and hydroxymethyl groups.

[0729] Polymerizable groups other than those with olefinic unsaturated bonds, preferably R in the repeating unit represented by formula (4) described later. 131 middle.

[0730] The amount of polymerizable groups other than those having olefinic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0731] -Polar switching group-

[0732] Polyimides can possess polar conversion groups such as acid-degradable groups. The acid-degradable groups in polyimides are analogous to the R groups in formula (2) above. 113 and R 114 The acid-decomposing groups described herein are the same, and the preferred methods are also the same.

[0733] Polar conversion groups, such as R contained in the repeating unit represented by formula (4) described later, are examples of such groups. 131 R 132 In the end of polyimide, etc.

[0734] -Acid Value-

[0735] When polyimide is used for alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more.

[0736] The acid value is preferably below 500 mg KOH / g, more preferably below 400 mg KOH / g, and even more preferably below 200 mg KOH / g.

[0737] When polyimide is supplied to a developing solution that uses an organic solvent as the main component (e.g., "solvent developing"), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g.

[0738] The acid value is determined by a known method, for example by the method described in JIS K 0070:1992.

[0739] From the viewpoint of balancing storage stability and developability, acid groups containing acid groups with a pKa of 0 to 10 are preferred as part of polyimide, and more preferably acid groups with a pKa of 3 to 8.

[0740] pKa is the value of the equilibrium constant Ka, expressed as its negative common logarithm, pKa, taking into account the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD / ChemSketch (registered trademark). pKa can also be referenced to the value published in the "Fifth Revised Edition of the Chemical Handbook (Basic Edition)" edited by the Chemical Society of Japan.

[0741] When the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0742] As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0743] -Phenolic hydroxyl-

[0744] From the viewpoint of achieving an appropriate development speed using alkaline developing solution, polyimide preferably has phenolic hydroxyl groups.

[0745] Polyimide can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0746] Phenolic hydroxyl groups are preferably included, for example, in the repeating unit represented by formula (4) described later. 132 Or R 131 middle.

[0747] The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0748] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferred to contain repeating units represented by the following formula (4).

[0749] [Chemical Formula 16]

[0750]

[0751] In equation (4), R 131 R represents a divalent organic group. 132 It represents a tetravalent organic group.

[0752] When it has polymerizable groups, the polymerizable groups can be located at R. 131 and R 132 At least one of them, as shown in formula (4-1) or formula (4-2) below, may also be located at the end of the polyimide.

[0753] Equation (4-1)

[0754] [Chemical Formula 17]

[0755]

[0756] In equation (4-1), R 133 The group is a polymerizable group, and the meanings of the other groups are the same as those in formula (4).

[0757] Equation (4-2)

[0758] [Chemical Formula 18]

[0759]

[0760] In equation (4-2), R 134 and R 135 At least one of them is a polymeric group, and when it is not a polymeric group, it is an organic group. The meanings of the other groups are the same as those in formula (4).

[0761] Examples of polymerizable groups include groups containing the aforementioned olefinic unsaturated bonds or crosslinking groups other than those containing the aforementioned olefinic unsaturated bonds.

[0762] R 131 This represents a divalent organic group. As a divalent organic group, it can be exemplified by R in formula (2). 111 The same organic groups have the same preferred range.

[0763] As R 131 Examples of diamines include the diamine residue 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.

[0764] 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 one molecule. Even more preferably, it is a diamine residue that does not contain an aromatic ring.

[0765] Examples of diamines containing a total of two or more ethylene glycol chains or propylene glycol chains in one 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 not limited to these.

[0766] Furthermore, R 131 Preferably, it is a group containing a group represented by formula (2-1), and more preferably a group represented by formula (2-1).

[0767] [Chemical Formula 19]

[0768]

[0769] In equation (2-1), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond or a divalent linker without an imide bond, and * represents a bonding site with other structures.

[0770] In equation (2-1), R 1 and R 2 Each group is preferably represented by the following formula (R1-1).

[0771] [Chemical Formula 20]

[0772]

[0773] In equation (R1-1), L R1 R represents an n+1 valence linker. R1 Each of the following groups independently represents an aromatic group, maleimide group, (meth)acryloyloxy group, or (meth)acrylamide group that is directly bonded to a vinyl group, where n represents an integer from 1 to 10, and * represents the bonding site with the oxygen atom in formula (2-1).

[0774] R R1 Each of the aromatic groups or maleimide groups, which are directly bonded to the vinyl group, is preferred to be a vinylphenyl group.

[0775] L R1 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - The group represented by at least one group in the group, preferably a hydrocarbon group or * 1 -C (=O) -L R2 -* 2 or* 1 -C(=O)NR N -L R2 -* 2 The group represented.

[0776] As mentioned above L R1 The hydrocarbon group in the form is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0777] The above L R2 The group represents a hydrocarbon group, preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms.

[0778] The above R N The preferred method is as described above.

[0779] The above* 1 The meaning of * is the same as the meaning of * in equation (R1-1). 2 R represents the expression (R1-1) R1 The bonding sites.

[0780] And, when R R1 When it is vinylphenyl, L R1 Preferably, it is an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group.

[0781] When R R1 When it is maleimide, LR1 Preferably, it is an alkylene group having 1 to 4 carbon atoms or composed of * 1 -C (=O) -L R2 -* 2 The group indicated.

[0782] When R R1 When it is (meth)acryloyloxy or (meth)acrylamide, L R1 Preferred to be made of * 1 -C(=O)NR N -L R2 -* 2 The group indicated.

[0783] n is preferably an integer from 1 to 4, more preferably 1 or 2, and more preferably 1.

[0784] In formula (2-1), L is preferably a single bond, -C(CH3)2-, -C(CF3)2-, -S(=O)2-, or 9,9-fluorene dimethyl. Furthermore, L being a single bond, -C(CH3)2-, or -C(CF3)2- is also one of the preferred embodiments of the present invention.

[0785] R 132 This represents a tetravalent organic group. As a tetravalent organic group, it can be exemplified by R in formula (2). 115 The same organic groups have the same preferred range.

[0786] For example, as R 115 The four connectors of the exemplified tetravalent organic group are bonded to the four -C (=O)- portions in the above formula (4) to form a fused ring.

[0787] R 132 Examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. As a specific example, R in formula (2) of a polyimide precursor can be cited. 115 Examples. From the perspective of the strength of organic membranes, R 132 Preferably, it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0788] R is also preferred 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, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the aforementioned (DA-1) to (DA-18). 132Examples of better choices can be found in (DAA-1) to (DAA-5).

[0789] The polyimide preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, more preferably 20% by mass or less.

[0790] To improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0791] To improve the storage stability of the composition, the main chain of the polyimide is preferably capped with a monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. Among these, monoamines are more preferred. Examples of preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-5-aminonaphthalene. -Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0792] -Imidization rate (ring-closure rate)-

[0793] 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 50% or more, more preferably 70% or more, and even more preferably 90% or more.

[0794] The upper limit of the imidization rate is not particularly limited; it can be below 100%.

[0795] The imidization rate described above was determined using the method described above.

[0796] Polyimide can contain R consisting of all repeating units 131 and R 132The repeating units represented by the above equation (4) with the same combination can also contain R consisting of two or more types. 131 and R 132 The repeating units represented by the above formula (4) can be different combinations. In addition to the repeating units represented by the above formula (4), polyimide may also contain other types of repeating units. For example, the repeating units represented by the above formula (2) can be cited as other types of repeating units.

[0797] Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine (with a portion replaced as a capping agent for a monoamine) at low temperature; by reacting a tetracarboxylic dianhydride (with a portion replaced as a capping agent for an anhydride, a monoacyl chloride, or a monoactive ester compound) with a diamine at low temperature; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (with a portion replaced as a capping agent for a monoamine) in the presence of a condensing agent; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acyl-chlorinating the remaining dicarboxylic acid and reacting it with a diamine (with a portion replaced as a capping agent for a monoamine), and then fully imidizing it using a known imidization reaction method; or by stopping the imidization reaction midway and introducing a partial imide structure; and by introducing a partial imide structure by mixing a fully imidized polymer with the polyimide precursor. Furthermore, other known methods for synthesizing polyimides can also be applied.

[0798] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural strength of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred.

[0799] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0800] 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. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0801] When the 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.

[0802] [Polybenzoxazole precursor]

[0803] Compounds described in paragraphs 0073 to 0095 of International Publication No. 2022 / 145355 as precursors of polybenzoxazole can be cited as examples. These descriptions are incorporated herein by reference.

[0804] [Polybenzoxazole]

[0805] As polybenzoxazoles, examples include compounds described in paragraphs 0101 to 0108 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0806] [Polyamide-imide precursor]

[0807] Compounds described in paragraphs 0104 to 0119 of International Publication No. 2022 / 145355 can be cited as precursors for polyamide-imide. These descriptions are incorporated herein by reference.

[0808] [Polyamide-imide]

[0809] As polyamide-imides, examples include compounds described in paragraphs 0125 to 0138 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0810] [Methods for manufacturing polyimide precursors, etc.]

[0811] Polyimide precursors, etc., are manufactured, for example, by the methods described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0812] 〔content〕

[0813] The content of a specific resin in the composition is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solids content of the composition. Furthermore, the content of the resin in the composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and still more preferably 95% by mass or less, relative to the total solids content of the composition.

[0814] The composition may contain only one specific resin or two or more specific resins. When it contains two or more specific resins, the total amount is preferably within the range described above.

[0815] The composition preferably contains at least two resins.

[0816] Specifically, the composition may contain two or more specific resins and other resins described below, or it may contain two or more specific resins, but preferably two or more specific resins.

[0817] When the composition contains two or more specific resins, for example, it is preferable to contain a structure derived from dianhydride as a polyimide precursor (R in formula (2) above). 115 Two or more different polyimide precursors.

[0818] <Other Resins>

[0819] The composition may contain the specific resin described above and other resins that are different from the specific resin (hereinafter also referred to as "other resins").

[0820] Other resins that can be cited include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins.

[0821] For example, by further adding (meth)acrylic resin, a composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

[0822] For example, by adding (meth)acrylic resin to the composition in place of the polymerizable compound described later, or by adding (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the composition, the solvent resistance of the pattern (cured product), etc., can be improved. This (meth)acrylic resin has a weight-average molecular weight of 20,000 or less and a high value of polymerizable groups (e.g., the molar content of polymerizable groups in 1g of resin is 1×10⁻⁶). -3 (more than moles / g).

[0823] When the composition contains other resins, the content of other resins relative to the total solid content of the 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.

[0824] When the composition contains other resins, the content of other resins 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 composition.

[0825] As a preferred embodiment of the composition, the content of other resins can also be set to be low. In the above embodiment, the content of other resins relative to the total solids content of the composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and still more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, and 0% by mass or more is acceptable.

[0826] The composition may contain only one other resin or two or more other resins. When it contains two or more specific resins, the total amount is preferably within the range described above.

[0827] <Polymerizing compounds>

[0828] The composition preferably contains a polymerizable compound.

[0829] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0830] [Free radical cross-linking agent]

[0831] The composition preferably contains a free radical crosslinking agent.

[0832] 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.

[0833] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from a reactivity point of view.

[0834] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, but more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may have three or more olefinic unsaturated bonds.

[0835] As compounds having two or more of the above-mentioned olefinic unsaturated bonds, compounds having 2 to 15 olefinic unsaturated bonds are preferred, compounds having 2 to 10 olefinic unsaturated bonds are more preferred, and compounds having 2 to 6 olefinic unsaturated bonds are even more preferred.

[0836] From the viewpoint of the film strength of the obtained pattern (cured product), the composition preferably contains compounds having two olefinic unsaturated bonds and compounds having three or more of the above-mentioned olefinic unsaturated bonds.

[0837] 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.

[0838] 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-fusion reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Furthermore, 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 preferred, and substitution reactions of unsaturated carboxylic acid esters or amides having leaving substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Furthermore, as other examples, compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers can be used instead of the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0839] The free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at atmospheric pressure. Examples of compounds having a boiling point of 100°C or higher at atmospheric pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0840] 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.

[0841] As free radical crosslinking agents, preferred are dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku Co., Ltd.)), A-TMMT (commercially available as SHIN-NAKAMURA CHEMICAL Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (Nippon Kayaku Co., Ltd.)), A-DPH (commercially available as SHIN-NAKAMURA CHEMICAL Co., Ltd.), and structures in which their (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0842] 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 pentylene groups, trifunctional acrylates TPA-330 with three isobutylene 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.

[0843] As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and urethane compounds having an ethylene oxide backbone described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418 are also preferred. Compounds having an amino or thioether structure within the molecule, as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238, can also be used as free radical crosslinking agents.

[0844] 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, and more preferably a free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol in the free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO.,LTD.

[0845] 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. As long as the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and developability. Furthermore, it has good polymerizability. The above acid value was determined according to the description in JIS K 0070:1992.

[0846] As a free radical crosslinking agent, a free radical crosslinking agent having at least one of the groups selected from urea bonds and urethane bonds is also preferred (hereinafter also referred to as "crosslinking agent U").

[0847] In this invention, the urea bond refers to the bond formed by *-NR. N -C(=O)-NR N -* indicates the key, R N Each symbol represents a hydrogen atom or a monovalent organic group independently, and * represents the bonding site with a carbon atom.

[0848] In this invention, the carbamate bond refers to the bond formed by *-OC(=O)-NR. N -* indicates the key, R NThe symbol represents a hydrogen atom or a monovalent organic group, and * indicates the bonding site with a carbon atom, respectively.

[0849] Compositions containing crosslinking agent U can sometimes improve chemical resistance, resolution, etc.

[0850] The crosslinking agent U may have only one urea bond or a carbamate bond, or it may have one or more urea bonds and one or more carbamate bonds, or it may have two or more urea bonds but no carbamate bonds, or it may have two or more carbamate bonds but no urea bonds.

[0851] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0852] When the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0853] When the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0854] The free radical polymerizable groups in the crosslinking agent U are not particularly limited, and examples include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0855] When the crosslinking agent U has more than two free radical polymerizable groups, the structures of each free radical polymerizable group can be the same or different.

[0856] The number of free radical polymerizable groups in the crosslinking agent U can be only 1 or more than 2, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0857] The free radical polymerizable group value (mass of compound per mole of free radical polymerizable groups) in crosslinking agent U is preferably 150-400 g / mol.

[0858] From the viewpoint of the chemical resistance of the cured product, the lower limit of the free radical polymerizability group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0859] From the viewpoint of reproducibility, the upper limit of the above-mentioned free radical polymerizability group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and particularly preferably 300 g / mol or less.

[0860] The polymerizability of the crosslinking agent U is preferably 210–400 g / mol, more preferably 220–400 g / mol.

[0861] The crosslinking agent U is preferably a structure represented by, for example, the following formula (U-1).

[0862] [Chemical Formula 21]

[0863]

[0864] In equation (U-1), R U1 A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR. N -, R N Z is a hydrogen atom or a monovalent organic group. U1 Z is an m-valent organic group. U2 X is an organic group with an n+1 valence, where X is a free radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0865] R U1 Hydrogen atoms, alkyl or aromatic hydrocarbon groups are preferred, and hydrogen atoms are more preferred.

[0866] R N Hydrogen atoms, alkyl or aromatic hydrocarbon groups are preferred, and hydrogen atoms are more preferred.

[0867] Z U1 Preferred radicals include hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, and -NR. N - or groups formed by bonding two or more of them, more preferably hydrocarbon groups or hydrocarbon groups combined with groups selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in the group.

[0868] As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. N It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0869] Z U2Preferred radicals include hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, and -NR. N - or groups formed by bonding two or more of them, more preferably hydrocarbon groups or hydrocarbon groups combined with groups selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in the group.

[0870] As the aforementioned hydrocarbon group, examples can be cited that are similar to those in Z. U1 The hydrocarbon groups mentioned above that have the same hydrocarbon group are preferred in the same way.

[0871] X is not particularly limited and may include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0872] n is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably 1 or 2, and particularly preferably 1.

[0873] m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0874] The crosslinking agent U is preferably composed of at least one of hydroxyl, alkeneoxy, amide and cyano groups.

[0875] From the viewpoint of the chemical resistance of the obtained cured film, the hydroxyl group can be an alcoholic hydroxyl group or a phenolic hydroxyl group, but an alcoholic hydroxyl group is preferred.

[0876] From the viewpoint of the chemical resistance of the obtained cured film, the alkene oxide is preferably an alkene oxide with 2 to 20 carbon atoms, more preferably an alkene oxide with 2 to 10 carbon atoms, even more preferably an alkene oxide with 2 to 4 carbon atoms, and even more preferably an ethene oxide or a propene oxide, and particularly preferably an ethylene oxide.

[0877] The alkene oxide can be included in the crosslinking agent U as a polyalkene oxide. In this case, the number of repetitions of the alkene oxide is preferably 2 to 10, more preferably 2 to 6.

[0878] The amide group refers to the group consisting of -C(=O)-NR N - indicates the key. R N As described above. When the crosslinking agent U has an amide group, the crosslinking agent U can contain, for example, RC(=O)-NR. N -* indicates a group or is composed of *-C(=O)-NR N-R represents a group. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0879] The crosslinking agent U can have two or more structures selected from the group consisting of hydroxyl, alkene (wherein, when constituting polyalkene, it is polyalkene), amide and cyano groups, but it is also preferred to have only one in the molecule.

[0880] The aforementioned hydroxyl, alkeneoxy, and cyano groups can exist at any position in the crosslinking agent U. However, from the viewpoint of chemical resistance, in the crosslinking agent U, at least one of the groups selected from the group consisting of the aforementioned hydroxyl, alkeneoxy, and cyano groups is preferably linked to at least one free radical polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1").

[0881] In particular, when the crosslinking agent U contains only one free radical polymerizable group, the free radical polymerizable group contained in the crosslinking agent U is preferably linked to at least one of the groups selected from hydroxyl, alkene, amide and cyano groups via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").

[0882] When the crosslinking agent U contains an alkene group (wherein, if it constitutes a polyalkene group, it is a polyalkene group) and has the aforementioned linking group L2-1 or the aforementioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or linking group L2-2 of the alkene group (wherein, if it constitutes a polyalkene group, it is a polyalkene group) is not particularly limited, but it is preferable to have a group represented by a hydrocarbon group, a free radical polymerizable group, or a combination thereof. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. Furthermore, the preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the aforementioned crosslinking agent U.

[0883] When the crosslinking agent U contains an amide group and has the aforementioned linking group L2-1 or L2-2, the structure bonded to the side opposite to the linking group L2-1 or L2-2 of the amide group is not particularly limited, but is preferably a group represented by a hydrocarbon group, a free radical polymerizable group, or a combination thereof. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. The preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the crosslinking agent U. Furthermore, in the above manner, the carbon atom side of the amide group can be bonded to the linking group L2-1 or L2-2, and the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or L2-2.

[0884] Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, the crosslinking agent U preferably has hydroxyl groups.

[0885] From the viewpoint of compatibility with heterocyclic polymers, the crosslinking agent U preferably contains aromatic groups.

[0886] The aromatic groups mentioned above are preferably directly bonded to the urea bonds or urethane bonds contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.

[0887] The aromatic group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, or a structure formed by these forming a fused ring, preferably an aromatic hydrocarbon group.

[0888] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 20 carbon atoms is more preferred, and a group formed by removing 2 or more hydrogen atoms from the benzene ring structure is even more preferred.

[0889] As the aforementioned aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. Examples of aromatic heterocycles in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetraazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings can be further fused with other rings, such as indole and benzimidazole.

[0890] Nitrogen, oxygen, or sulfur atoms are preferred as heteroatoms contained in the aforementioned aromatic heterocyclic groups.

[0891] The aromatic groups mentioned above are preferably included, for example, in the following linking groups: linking groups that link two or more free radical polymerizable groups and contain urea bonds or urethane bonds; or linking groups that link at least one of the groups selected from the group consisting of hydroxyl, alkoxy, amide and cyano groups and at least one free radical polymerizable group contained in the crosslinking agent U.

[0892] The number of atoms (linking chain length) between the urea bond or urethane bond in the crosslinking agent U and the free radical polymerizable group is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.

[0893] When the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, or contains two or more free radical polymerizable groups, or contains two or more urea bonds or urethane bonds and two or more free radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bonds or urethane bonds and the free radical polymerizable groups shall be within the above range.

[0894] In this specification, "the number of atoms (linkage chain length) between the urea bond or urethane bond and the polymerizable group" refers to the shortest (minimum number of atoms) path connecting the two atoms or groups of atoms that are the linking objects. For example, in the structure represented by the following formula, the number of atoms (linkage chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy) is 2.

[0895] [Chemical Formula 22]

[0896]

[0897] [Axis of symmetry]

[0898] The crosslinking agent U is preferably a compound without a symmetry axis.

[0899] The absence of a symmetry axis in crosslinking agent U means that it is a compound that is asymmetrical from left to right, and does not possess an axis that would allow the creation of molecules identical to the original molecules by rotating the entire compound. Furthermore, when marking the structural formula of crosslinking agent U on paper, the absence of a symmetry axis in crosslinking agent U means that its structural formula cannot be marked as having a symmetry axis.

[0900] It is believed that since the crosslinking agent U does not have a symmetry axis, the aggregation of crosslinking agents U in the composite film is suppressed.

[0901] [Molecular weight]

[0902] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0903] The method of manufacturing crosslinking agent U is not particularly limited, but for example, it can be obtained by reacting a compound having a free radical polymerizable compound and an isocyanate group with a compound having at least one of hydroxyl or amino groups.

[0904] The following are specific examples of crosslinking agent U, but crosslinking agent U is not limited to these.

[0905] [Chemical Formula 23]

[0906]

[0907] [Chemical Formula 24]

[0908]

[0909] [Chemical Formula 25]

[0910]

[0911] From the viewpoint of pattern resolution and film stretchability, the composition preferably uses difunctional methacrylates or acrylates.

[0912] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, and 1,6-hexanediol diacrylate can be used. 1,6-Hexanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, dimethylol-tricyclodecane dimethacrylate, 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-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0913] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0914] From the viewpoint of suppressing warping of the pattern (cured product), the composition preferably uses a monofunctional free radical crosslinking agent as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and allyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred.

[0915] 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.

[0916] When a free radical crosslinking agent is present, the content of the free radical crosslinking agent relative to the total solid content of the composition is preferably more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0917] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used together, it is preferable that their combined dosage is within the range mentioned above.

[0918] [Other crosslinking agents]

[0919] The composition also preferably contains other crosslinking agents that are different from the free radical crosslinking agents described above.

[0920] 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 reaction (forming covalent bonds with other compounds in the composition or their reaction products) through photosensitization by the aforementioned photoacid-producing agents or photoalkali-producing agents. More preferably, they are compounds having multiple groups within the molecule that promote the reaction (forming covalent bonds with other compounds in the composition or their reaction products) through the action of acids or bases.

[0921] 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.

[0922] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0923] [Polymerization initiator]

[0924] The composition preferably contains a polymerization initiator.

[0925] The polymerization initiator can be either a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferred to contain a photopolymerization initiator.

[0926] 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 a reactive agent that reacts with a photoexcited sensitizer to generate active free radicals.

[0927] The photoradical polymerization initiator preferably contains at least one initiator having a concentration 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 (Cary-5 spectrophotometer manufactured by Varian) and with ethyl acetate solvent at a concentration of 0.01 g / L.

[0928] As a photoradical polymerization initiator, 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, thio 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.

[0929] 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, may be cited. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) may also be preferably used in commercially available products.

[0930] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators as described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators as described in Japanese Patent No. 4225898 can be used, as these contents are incorporated herein by reference.

[0931] 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.

[0932] 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.

[0933] 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 preferably. This content is incorporated herein by reference.

[0934] Oxime compounds are more preferably selected as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be further improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0935] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science. The compounds described in andTechnology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent Application Publication No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and the compounds described in International Publication No. 2013 / 167515, etc., are included in this specification.

[0936] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy)imino)but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one. In the composition, the oxime compound is particularly preferred as a photoradical polymerization initiator. The oxime compound used as a photoradical polymerization initiator has an intramolecular linking group >C=NOC(=O)-.

[0937] [Chemical Formula 26]

[0938]

[0939] 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). Oxime compounds with the following structures can also be used.

[0940] [Chemical Formula 27]

[0941]

[0942] [Chemical Formula 28]

[0943]

[0944] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring, oxime compounds having at least one benzene ring in which a carbazole ring forms a naphthalene ring skeleton, and oxime compounds having fluorine atoms can also be used.

[0945] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, are also permitted to be used. These contents are incorporated herein by reference.

[0946] Furthermore, compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Publication No. 2023-058585 can also be used as photopolymerization initiators. This description is incorporated into the specification of this application.

[0947] When the composition contains a photopolymerization initiator, its content relative to the total solids content of the composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0948] In addition, photopolymerization initiators can sometimes also function as thermal polymerization initiators. Therefore, heating with ovens, hot plates, etc., can sometimes further promote crosslinking using photopolymerization initiators.

[0949] [Sensitizer]

[0950] The composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in its electronically excited state comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. Consequently, the thermal free radical polymerization initiator or photofree radical polymerization initiator undergoes a chemical change and decomposes, generating free radicals, acids, or bases.

[0951] As usable sensitizers, compounds such as benzophenone, michidone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0952] 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-dimethylaminoindanone. Benzylindanone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl 7-Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate 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.

[0953] In addition, other sensitizing pigments can also be used.

[0954] 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.

[0955] When the composition contains a sensitizer, the content of the sensitizer relative to the total solid content of the 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.

[0956] [Chain transfer agent]

[0957] The composition 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 intramolecular -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds with thiocarbonyl sulfhydryl 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.

[0958] 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.

[0959] When the 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 in the composition. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total content falls within the above range.

[0960] Furthermore, having two or more polymerization initiators in the composition is also one of the preferred embodiments of the present invention.

[0961] Specifically, the composition 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-generating agent.

[0962] By including photopolymerization initiators and thermal polymerization initiators (described later), it is sometimes possible to form patterns using exposure and to easily perform free radical polymerization during curing using the heating process described later, thereby improving properties such as chemical resistance.

[0963] 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.

[0964] By incorporating photoradical polymerization initiators and photoacid-producing agents, properties such as resolution can sometimes be improved.

[0965] 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.

[0966] [Thermal polymerization initiator]

[0967] 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.

[0968] As thermal free radical polymerization initiators, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated in this specification, can be cited.

[0969] When the composition contains a thermal polymerization initiator, its content relative to the total solids content of the 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 composition may contain only one thermal polymerization initiator or may contain two or more. When it contains two or more thermal polymerization initiators, the total amount is preferably within the above range.

[0970] <Alkali-producing agent>

[0971] The composition may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of producing alkali through physical or chemical action. Preferred alkali-generating agents include thermal alkali-generating agents and photo-alkali-generating agents.

[0972] In particular, when the composition contains a heterocyclic polymer precursor, the composition preferably contains an alkali-generating agent. By containing a thermal alkali-generating agent, the cyclization reaction of the precursor can be promoted by heating, thereby resulting in a material with good mechanical properties or chemical resistance of the cured product, such as the performance of an interlayer insulating film for a rewiring layer contained in a semiconductor package.

[0973] As an alkali-producing agent, it can be either an ionic or a nonionic alkali-producing agent. Examples of bases produced from the alkali-producing agent include, for instance, secondary and tertiary amines.

[0974] The alkali-generating agent is not particularly limited, and known alkali-generating agents can be used. Examples of known alkali-generating agents include, for instance, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imine salts, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0975] Specific examples of nonionic alkali-generating agents include the compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0976] The following compounds can be cited as alkali-producing agents, but are not limited to these.

[0977] [Chemical Formula 29]

[0978]

[0979] The molecular weight of the nonionic alkali-generating agent is preferably below 800, more preferably below 600, and even more preferably below 500. The lower limit is preferably above 100, more preferably above 200, and even more preferably above 300.

[0980] Specific examples of preferred compounds as ionic alkali-generating agents include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0981] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[0982] [Chemical Formula 30]

[0983]

[0984] The following compounds can be cited as specific examples of imine salts, but are not limited to these.

[0985] [Chemical Formula 31]

[0986]

[0987] 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.

[0988] Examples of amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, 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.

[0989] When the 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 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.

[0990] One or more alkali-producing agents can be used. When two or more are used, the total amount is preferably within the above range.

[0991] <Solvent>

[0992] The composition preferably contains a solvent.

[0993] 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.

[0994] 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-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid, alkyl 3-ethoxypropionic acid). Alkyl esters of 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[0995] Examples of preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0996] Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0997] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred cyclic hydrocarbons.

[0998] As a sulfoxide, dimethyl sulfoxide can be cited as a preferred sulfoxide.

[0999] As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine are among the preferred amides.

[1000] Examples of preferred urea types include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[1001] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[1002] From the perspective of improving the properties of the coating surface, it is also preferable to use a mixture of two or more solvents.

[1003] In this invention, the solvent is preferably selected from one of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucanone, and dihydro L-glucanone, or a mixture of two or more solvents. More preferably, the solvent is selected from at least one of the following: γ-butyrolactone, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. Particularly preferred methods include the use of dimethyl sulfoxide with γ-butyrolactone, dimethyl sulfoxide with γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone with ethyl lactate. Further addition of approximately 1 to 10% by mass relative to the total mass of these solvents is also a preferred method of the invention.

[1004] In particular, from the viewpoint of the storage stability of the composition, including γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and can be 100% by mass. The above content can be determined taking into account the solubility of heterocyclic polymers and other components contained in the composition.

[1005] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used together, the total mass of the solvent preferably contains 60-90% by mass of γ-valerolactone and 10-40% by mass of dimethyl sulfoxide, more preferably 70-90% by mass of γ-valerolactone and 10-30% by mass of dimethyl sulfoxide, and even more preferably 75-85% by mass of γ-valerolactone and 15-25% by mass of dimethyl sulfoxide.

[1006] From a coating properties perspective, the solvent content is preferably set at a total solids concentration of 5-80% by mass, more preferably at a total solids concentration of 5-75% by mass, even more preferably at a total solids concentration of 10-70% by mass, and even more preferably at a total solids concentration of 20-70% by mass. The solvent content can be adjusted according to the required coating thickness and coating method. When two or more solvents are contained, it is preferable that their total content is within the above range.

[1007] <Metal Adhesion Modifier>

[1008] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, the composition preferably contains a metal adhesion modifier. Examples of metal adhesion modifiers 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.

[1009] [Silane coupling agent]

[1010] 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, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. The following compounds are also preferred as silane coupling agents. In the following formula, Me represents methyl and Et represents ethyl. Furthermore, the following R can be a structure derived from the end-capping isocyanate group. As end-capping agents, they can be selected according to the desorption temperature, and examples include alcohol compounds, phenolic compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of setting the desorption 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.).

[1011] [Chemical Formula 32]

[1012]

[1013] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3- Acryloyloxypropyltrimethoxysilane, 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-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[1014] Furthermore, as a silane coupling agent, compounds of oligomer type having multiple alkoxysilyl groups can also be used.

[1015] Examples of this type of oligomer include compounds containing repeating units represented by the following formula (S-1).

[1016] [Chemical Formula 33]

[1017]

[1018] 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.

[1019] R S1 The structure containing a polymerizable group is preferred. 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 groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl groups), (meth)acrylamido groups, and (meth)acryloyloxy groups. Vinylphenyl, (meth)acrylamido, or (meth)acryloyloxy groups are preferred, vinylphenyl or (meth)acryloyloxy groups are more preferred, and (meth)acryloyloxy groups are even more preferred.

[1020] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[1021] n represents an integer from 0 to 2, preferably 1.

[1022] Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer type compound can be the same.

[1023] Here, in the oligomer-type compound, among the plurality of repeating units represented by formula (S-1), it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two.

[1024] As for this type of oligomer compound, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[1025] [Aluminum-based adhesive additives]

[1026] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate diisopropoxide aluminum.

[1027] As other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated in this specification.

[1028] The content of the metal adhesion modifier 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, relative to 100 parts by weight of the heterocyclic polymer. By setting the content to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting the content to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. The metal adhesion modifier may be only one type or two or more types. When two or more types are used, it is preferable that their total content is within the above range.

[1029] <Migration Inhibitor>

[1030] The composition preferably further contains a migration inhibitor. By containing a migration inhibitor, for example, when the 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.

[1031] As migration inhibitors, there are no particular limitations, 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 and 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.

[1032] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[1033] Other migration inhibitors may include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are incorporated herein by reference.

[1034] The following compounds can be cited as specific examples of migration inhibitors.

[1035] [Chemical Formula 34]

[1036]

[1037] When the lipid composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to the total solid content of the composition.

[1038] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the range mentioned above.

[1039] <Polymerization Inhibitor>

[1040] The composition 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.

[1041] Specific compounds that can be used 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.

[1042] When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, relative to the total solid content of the composition.

[1043] There may be only one type of polymerization inhibitor or two or more types. When there are two or more types of polymerization inhibitors, it is preferable that their total number is within the range mentioned above.

[1044] [Urea compounds, carbodiimide compounds, isourea compounds]

[1045] From the viewpoint of elongation at break and adhesion to metal or resin layers, the composition may contain at least one compound selected from the group consisting of compounds having urea bonds (urea compounds), compounds having carbodiimide structures (carbodiimide compounds), and compounds having isourea bonds (isourea compounds) (hereinafter also referred to as "urea compounds, etc.").

[1046] In these compositions, the composition preferably also contains a compound having a urea bond.

[1047] The urea compounds mentioned here do not include the polymerizable compounds mentioned above, or compounds corresponding to silane coupling agents.

[1048] Examples of urea compounds include those described in paragraphs 0334 to 0339 of International Publication No. 2022 / 070730.

[1049] Specific examples of urea compounds include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, etc., but are not limited to these.

[1050] The total content of urea compounds, etc., relative to 100 parts by weight of heterocyclic polymer is preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 8.0 parts by weight, and even more preferably 1.0 to 6.0 parts by weight.

[1051] Urea compounds can be used alone or in combination with two or more. When two or more alkalis are used in combination in an alkaline treatment solution, their total content is preferably within the range mentioned above.

[1052] <Light Absorber>

[1053] The composition also preferably contains a compound (light absorber) that reduces the absorbance of its exposure wavelength due to exposure.

[1054] 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 are included in this specification.

[1055] Furthermore, including a photochromic compound as a light absorber is also one of the preferred embodiments of the present invention. A photochromic compound is a compound whose molecular geometry changes due to light absorption, thereby altering its absorption spectrum.

[1056] The following are specific examples of photochromic compounds, but the present invention is not limited thereto.

[1057] [Chemical Formula 35]

[1058]

[1059] The content of the light absorber relative to the total solid content of the composition 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.

[1060] <Other Additives>

[1061] The composition 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 film properties and other properties 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, which are incorporated herein by reference. When formulating these additives, it is preferable that their total content be set to 3% by mass or less of the solid components of the composition.

[1062] <Characteristics of the Composition>

[1063] The viscosity of the composition can be adjusted by the concentration of its solid components. From the viewpoint of coating film thickness, 1,000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000mm 2 / s~10,000mm 2 / s, further optimized to 2,500mm 2 / s~8,000mm 2 / s. As long as it remains within the above range, a highly uniform coating film can be easily obtained. For 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.

[1064] The Young's modulus of the coated film containing the composition is preferably 3.8 GPa or higher after heating at 230°C for 2 hours.

[1065] The Young's modulus is preferably 3.9 GPa or higher, more preferably 4.0 GPa or higher. The upper limit of the Young's modulus is not particularly limited, for example, it is preferably 10.0 GPa or lower.

[1066] Here, the coating method for the resin composition used in the Young's modulus determination is not particularly limited, as long as the distance from the substrate to the film surface (i.e., the coating film thickness) is, for example, 20 μm, a spin coating method can be used. Furthermore, when it is difficult to form a film with the aforementioned 20 μm distance by a single spin coating, multiple spin coatings can be performed. Moreover, even so, when it is difficult to form a film with the aforementioned 20 μm distance by spin coating, a coating method can be appropriately 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.

[1067] When the composition contains a solvent, drying is preferably performed after the above coating. In this case, the distance from the substrate to the surface of the dried film is 20 μm.

[1068] Drying is preferably carried out until the amount of solvent in the membrane reaches less than 0.5% by mass.

[1069] The drying conditions are not particularly limited and can be achieved by heating. Furthermore, when heating alone is insufficient for thorough drying, reduced pressure can be applied.

[1070] Drying can be carried out under atmospheric conditions. However, when the resin composition contains components that are easily modified by oxygen, it can also be carried out under conditions such as displacement by inert gases like nitrogen or under vacuum.

[1071] The drying method is not particularly limited, but examples include hot plates. However, when the aforementioned pressure reduction or inert gas replacement is required, ovens with pressure reduction function or ovens with gas replacement function can also be used.

[1072] When drying is performed using heat, the heating temperature (drying temperature) can be, for example, 100°C. However, when it is difficult to dry at 100°C, the drying temperature can be appropriately changed between 70°C and 130°C, preferably between 90°C and 120°C, depending on the type of solvent contained in the resin composition.

[1073] When drying is performed using heat, the drying time (the time supplied to the above-mentioned heating temperature) can be, for example, 5 minutes. However, if it is difficult to dry within 5 minutes, the drying time can be appropriately changed between 30 seconds and 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the resin composition.

[1074] When drying is performed using heat, the heating rate is not particularly limited, and can be set to, for example, 5°C / min. When drying is difficult to perform at the above heating rate, the heating rate can be appropriately changed between 1 and 12°C / min or 2 and 10°C / min, depending on the type of solvent contained in the resin composition.

[1075] Using a stepper motor (Nikon NSR 2005 i9C), at 500 mJ / cm 2 The exposure energy exposed i-rays to the entire surface of the coated film obtained by the above coating and drying as needed.

[1076] A cured product is prepared by heating the exposed composition layer (resin layer) at 230°C for 2 hours.

[1077] The film obtained by applying the resin composition should be heated while avoiding exposure as much as possible. Furthermore, contact with solvents such as developing solutions should also be avoided as much as possible.

[1078] The above heating can be carried out in a nitrogen environment using an oven.

[1079] The pressure during the heating process is set to 1 atmosphere (101,325 Pa).

[1080] The heating rate described above can be set to, for example, 10°C / min. When drying is difficult at the above heating rate, the heating rate can be appropriately changed between 1 and 12°C / min or 2 and 10°C / min, depending on the type of solvent contained in the resin composition.

[1081] The heating time (exposure time to 230°C) in the above heating process is set to 2 hours.

[1082] The Young's modulus of the cured material was measured after cooling to 25°C.

[1083] The Young's modulus was determined according to the method described in JIS K 7161-1:2014.

[1084] <Limitations Regarding Substances Contained in the Composition>

[1085] The moisture content of the composition 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 composition is improved.

[1086] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[1087] From an insulating point of view, the metal content of the composition 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 as complexes of organic compounds with metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above-mentioned range.

[1088] Furthermore, as a method to reduce metal impurities accidentally included in the composition, the following methods can be cited: selecting raw materials with low metal content as raw materials for constituting the composition, filtering the raw materials constituting the composition with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[1089] Regarding the composition, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. Of this, the halogen atom content existing in the form of halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges.

[1090] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[1091] As a container for the composition, conventionally known containers can be used. For the purpose of preventing impurities from contaminating the raw materials or composition, multi-layered bottles with an inner wall composed of six types of six-layered resins, or bottles with a seven-layered structure formed by six types of resins, are also preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[1092] <Preparation of the Composition>

[1093] The composition can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out by conventionally known methods.

[1094] Examples of mixing methods include mixing using stirring blades, mixing using a ball mill, and mixing by rotating a tank.

[1095] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[1096] For the purpose of removing foreign matter such as dust or particles from the composition, filtration using a filter is preferred. Regarding the filter pore size, for example, 5 μm or less is preferred, more preferably 1 μm or less, further preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be a filter pre-cleaned with an organic solvent. In the filter 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 connected in series as the first stage and an HDPE filter with a 0.2 μm pore size as the second stage. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a circulating filtration. Filtration can also be performed after pressurization. When filtration is performed after pressurization, the pressurized pressure is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[1097] In addition to filtration using filters, impurity removal can also be performed 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.

[1098] After filtration, the composition filled in the bottle can be degassed under reduced pressure.

[1099] Example

[1100] 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 without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[1101] <Resin Synthesis>

[1102] [Synthesis Example: Synthesis of Polymer 1]

[1103] 20.80 g (40 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy) phthalic anhydride was dissolved in 70 g of N-methylpyrrolidone (NMP). Next, 3.81 g (17.6 mmol) of 3,3'-dihydroxybenzidine and 3.74 g (17.6 mmol) of 2,2'-dimethylbenzidine were dissolved in 50 g of NMP. The mixture was added dropwise over 1 hour at a temperature of 10°C–25°C, and stirred at 25°C for 30 minutes. Then, 10 g of toluene was added, and the mixture was allowed to react at 200°C for 4 hours under nitrogen atmosphere, followed by cooling to 25°C. Next, 15.3 g (50 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. The mixture was reacted at 95°C for 15 hours, then cooled to 25°C and diluted with 120 g of tetrahydrofuran. The reaction mixture was then added dropwise to a mixture of 1.8 L of methanol and 0.6 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 8 hours. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polymer 1. Polymer 1 is a resin having repeating units represented by the following formula. The subscripts in parentheses of the repeating units indicate the molar ratio of each repeating unit. 1 H-NMR spectroscopy determined the structure of the repeating unit. Polymer 1 has a weight-average molecular weight of 25,000, a number-average molecular weight of 10,500, and an imidization rate of over 99%.

[1104] [Chemical Formula 36]

[1105]

[1106] [Synthesis Example: Synthesis of Polymer 2]

[1107] -Synthesis of diamine 2a for polymer 2 synthesis-

[1108] 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a flask. 98.21 g (450 mmol) of di-tert-butyl dicarbonate was added dropwise under ice-cooling. After the addition was complete, the mixture was stirred at 60 °C for 5 hours. After the reaction was complete, the mixture was cooled to room temperature, and then 35 mg of 2,2,6,6-tetramethylpiperidine 1-oxy radical, 68.68 g (450 mmol) of p-chloromethylstyrene, 74.63 g (540 mmol) of potassium carbonate, and 8.96 g (54.0 mmol) of potassium iodide were added. The mixture was stirred at 60 °C for 3 hours. After the reaction was complete, the mixture was filtered by vacuum filtration, and the filtrate was added dropwise to 500 mL of water. Since white crystals precipitated, the precipitated solid was recovered by vacuum filtration. The obtained white solid was purified by recrystallization using 1000 mL of acetone at 60 °C. 125 g (yield 85.6%) of the following intermediate 2b was obtained.

[1109] The structure of 2b is shown below. (From...) 1 H-NMR spectroscopy confirmed the following structure.

[1110] 1 H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 8.04-7.94 (s, 2H), 7.75-7.64 (d, 2H), 7.56-7.42 (m, 8H), 7.27-7.20 (d ,2H),7.19-7.12(d,2H),6.79-6.64(2H),5.89-5.77(2H),5.30-5.15(6H),1.49-1.43(s,18H)

[1111] [Chemical Formula 37]

[1112]

[1113] 75.0 g (115.6 mmol) of 2b and 500 mL of dichloromethane were mixed in a 1 L flask. After adding 131.8 g (1156 mmol) of trifluoroacetic acid at room temperature, the mixture was stirred at 40 °C for 5 hours. After the reaction was complete, 250 mL of methanol was added dropwise under ice-cooling, followed by 117.0 g (1156 mmol) of triethylamine. Since pale yellow crystals precipitated, the solid was recovered by filtration. Resuspension washing with 750 mL of methanol yielded 40.5 g (73% yield) of (2a). The structure of 2a is shown below. 1 H-NMR spectroscopy confirmed the following structure.

[1114] 1H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 7.53-7.45 (s, 8H), 7.05-6.98 (d, 2H), 6.92-6.85 (d, 2H), 6.79 -6.63(4H),5.89-5.78(d,2H),5.29-5.22(d,2H),5.20-5.13(s,4H),4.92-4.64(4H)

[1115] [Chemical Formula 38]

[1116]

[1117] -Synthesis of Polymer 2-

[1118] A solution was prepared by dissolving 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy) phthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxy radical in 120 g of N-methylpyrrolidone (NMP). Subsequently, 5.50 g (25.9 mmol) of 2,2'-dimethylbenzidine and 11.62 g (25.9 mmol) of 2a were dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at 0–10 °C. After stirring at 25 °C for 60 minutes, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the reaction was carried out at 80 °C for 4 hours. After the reaction was complete, the solution was cooled to 25 °C and diluted with 200 g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water. After stirring for 15 minutes, the polyimide resin was filtered. Then, the resin was re-slurryed with 1 L of water and filtered, 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 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain polymer 2. Polymer 2 is a resin having repeating units represented by the following formula. The subscripts in parentheses of the repeating units indicate the molar ratio of each repeating unit. Polymer 2 has a weight-average molecular weight of 25,000, a number-average molecular weight of 12,500, and an imidization rate of over 99%. 1 H-NMR spectroscopy determined the structure of the repeating unit.

[1119] [Chemical Formula 39]

[1120]

[1121] [Synthetic Examples: Synthesis of Polymers 5 to 7]

[1122] Polymers 5 through 7 were synthesized using the same method as polymer 2, except that the raw materials used were appropriately modified.

[1123] Polymers 5 through 7 are resins having repeating units represented by the following formula. 1 ¹H-NMR spectroscopy determined the structure of each repeating unit. In the following structures, the subscripts in parentheses indicate the molar ratio of each structure. The weight-average molecular weight, number-average molecular weight, and imidization rate of these resins are listed in the table below.

[1124] [Chemical Formula 40]

[1125]

[1126] [Table 1]

[1127]

[1128] [Synthetic Example: Synthesis of Polymer 3]

[1129] 10.4 g (47.6 mmol) of pyromellitic anhydride, 10.6 g (20.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diethylene glycol dimethyl ether (Diglyme) were mixed and stirred at 60 °C for 5 hours to prepare a diester of pyromellitic anhydride and 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) with 2-hydroxyethyl methacrylate. Then, the mixture was cooled to -20 °C, and 17.70 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.

[1130] Next, a solution obtained by dissolving 19.3 g (60.5 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over a period of 2 hours. Then, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor was precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 °C for 2 days to obtain polyimide precursor (polymer 3). The obtained polyimide precursor (polymer 3) had a weight-average molecular weight (Mw) of 25,000 and a number-average molecular weight (Mn) of 10,000. It is speculated that the polyimide precursor (polymer 3) has a structure containing two repeating units represented by the following formula (polymer 3). The subscripts in parentheses of the repeating units indicate the molar ratio of each repeating unit. Polymer 3 has a weight-average molecular weight of 25,000, a number-average molecular weight of 10,000, and an imidization rate of less than 5%.

[1131] [Chemical Formula 41]

[1132]

[1133] [Synthetic Example: Synthesis of Polymer 4]

[1134] 7.43 g (34.0 mmol) of pyromellitic anhydride, 17.7 g (34.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diethylene glycol dimethyl ether were mixed and stirred at 60 °C for 5 hours to prepare a diester of pyromellitic anhydride and 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) with 2-hydroxyethyl methacrylate. Then, the mixture was cooled to -20 °C, and 17.70 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.

[1135] Next, a solution obtained by dissolving 12.7 g (59.8 mmol) of 2,2'-dimethylbenzidine in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over a period of 2 hours. Then, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor was precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 °C for 2 days to obtain polyimide precursor (polymer 4). The obtained polyimide precursor (polymer 4) had a weight-average molecular weight (Mw) of 25,000 and a number-average molecular weight (Mn) of 9,950. It is speculated that the polyimide precursor (polymer 4) has a structure containing two repeating units represented by the following formula (polymer 4). The subscripts in parentheses of the repeating units indicate the molar ratio of each repeating unit. Polymer 4 has a weight-average molecular weight of 25,000, a number-average molecular weight of 9,950, and an imidization rate of less than 5%.

[1136] [Chemical Formula 42]

[1137]

[1138] [Synthetic Example: Synthesis of Polymer 8]

[1139] 23.5 g (75.7 mmol) of 4,4'-oxophthalic dianhydride (ODPA) and 22.3 g (75.7 mmol) of bis(phthalic dianhydride) (BPDA) were added to a separating flask, along with 39.7 g of 2-hydroxyethyl methacrylate (HEMA) and 136.8 g of tetrahydrofuran. The mixture was stirred at room temperature (25 °C), and 24.7 g of pyridine was added while stirring to obtain the reaction mixture. After the exothermic reaction ceased, the mixture was allowed to cool naturally to room temperature and left to stand for 16 hours.

[1140] Next, while ice-cooled, a solution obtained by dissolving 62.5 g of dicyclohexylcarbodiimide (DCC) in 61.6 g of tetrahydrofuran was added to the reaction mixture over a period of 40 minutes with stirring. Then, a solution obtained by suspending 27.6 g (137.8 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 119.7 g of tetrahydrofuran was added to the reaction mixture over a period of 60 minutes with stirring. After stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirring for 1 hour, followed by the addition of 136.8 g of tetrahydrofuran. The precipitate formed in the reaction mixture was removed by filtration, thus obtaining the reaction solution.

[1141] The obtained reaction solution was added to 716.2 g of ethanol, generating a precipitate composed of crude polymer. The crude polymer was filtered off and dissolved in 403.5 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470 g of water to precipitate the polymer, and the precipitate was filtered off. Next, the obtained polyimide precursor was dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (polymer 8). The obtained polyimide precursor (polymer 8) had a weight-average molecular weight (Mw) of 25,300 and a number-average molecular weight (Mn) of 10,150. It is presumed that the polyimide precursor (polymer 8) has a structure containing two repeating units represented by the following formula (polymer 8). The subscripts in parentheses of the repeating units indicate the molar ratio of each repeating unit. Polymer 8 has a weight-average molecular weight of 25,000, a number-average molecular weight of 10,150, and an imidization rate of 20%.

[1142] [Chemical Formula 43]

[1143]

[1144] [Synthetic Example: Synthesis of Polymers 9-15]

[1145] Polymers 9-15 were synthesized using the same method as polymers 3 and 4, with appropriate changes to the raw materials used. Each polymer is a resin having repeating units represented by the following formula. 1 H-NMR spectroscopy determined the structure of each repeating unit. In the following structures, the subscripts in parentheses indicate the molar ratio of each structure.

[1146] [Chemical Formula 44]

[1147]

[1148] [Chemical Formula 45]

[1149]

[1150] [Chemical Formula 46]

[1151]

[1152] [Table 2]

[1153]

[1154] <Example>

[1155] In each embodiment, the components listed in the table below were mixed to obtain compositions for forming each insulating pattern A.

[1156] Specifically, the content of each component recorded in the table is set as the amount (parts by mass) recorded in the "parts by mass" column of each column of the table.

[1157] The composition for forming insulating pattern A and the comparative composition were pressure filtered using a polypropylene filter with a pore width of 0.45 μm.

[1158] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[1159] [Table 3]

[1160]

[1161] [Table 4]

[1162]

[1163] The detailed information of each component recorded in the table is as follows.

[1164] [Polymer (Resin)]

[1165] • Polymers 1 to 8: Polymers 1 to 8 synthesized in the above manner

[1166] [Polymerizing compounds]

[1167] • Polymerizable compound 1: A compound with the following structure

[1168] • Polymerizable compound 2: Compounds with the following structures (in the following structures, the numbers indicate the molar ratio of each structure).

[1169] [Chemical Formula 47]

[1170]

[1171] [Polymerization initiator]

[1172] • Polymerization initiators 1-4: Compounds with the following structures

[1173] [Chemical Formula 48]

[1174]

[1175] [Migration Inhibitor]

[1176] • Migration Inhibitor 1: Compounds with the following structure

[1177] [Chemical Formula 49]

[1178]

[1179] [Metal adhesion modifier]

[1180] • Metal adhesion modifier 1: A compound with the following structure

[1181] [Chemical Formula 50]

[1182]

[1183] [Light absorber]

[1184] • Light absorber 1: A compound with the following structure

[1185] [Chemical Formula 51]

[1186]

[1187] [Organotitanium compounds]

[1188] Organotitanium compound 1: Compounds with the following structure

[1189] [Chemical Formula 52]

[1190]

[1191] [Polymerization inhibitor]

[1192] • Polymerization inhibitor 1: A compound with the following structure

[1193] [Chemical Formula 53]

[1194]

[1195] [Alkali-producing agent]

[1196] Alkali-producing agent 1: Compounds with the following structure

[1197] [Chemical Formula 54]

[1198]

[1199] [Solvent]

[1200] Solvent 1: GBL (γ-butyrolactone)

[1201] Solvent 2: NMP (N-methyl-2-pyrrolidone)

[1202] Solvent 3: DMSO (dimethyl sulfoxide)

[1203] <Evaluation>

[1204] [Evaluation of quality reduction rate]

[1205] In each embodiment, the resin 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 on a hot plate at 100°C for 5 minutes. A stepper (Nikon NSR 2005 i9C) was used at 500 mJ / cm². 2 The obtained resin composition layer was exposed to i-rays at an exposure energy of [energy value missing]. After the exposure, cyclopentanone was used as the developer for 60 seconds, and the layer was rinsed with PGMEA for 30 seconds.

[1206] The above-washed resin composition layer (resin layer) was heated in a nitrogen environment at a heating rate of 10°C / min to 230°C and then heated for 3 hours. The cured resin layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution and then 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 determined using a TG-DTA2500 manufactured by NETZSCH Japan kk under the following conditions.

[1207] -Determination Conditions-

[1208] Under nitrogen conditions, the temperature conditions were changed in the following order (1) to (2), the mass before (1) (mass A) and the mass after (2) (mass B) were measured, and the mass reduction rate was calculated by the following formula.

[1209] (1) Increase the temperature from 25°C to 250°C at a rate of 10°C / minute, and maintain the temperature at 250°C for 1 hour.

[1210] (2) Cool to 25°C

[1211] Mass reduction rate (%) = (1 - mass B / mass A) × 100

[1212] The evaluation should be conducted according to the following evaluation criteria, and the evaluation results should be recorded in the "Reduction Rate of Quality" column of the table.

[1213] -Evaluation Criteria-

[1214] A: The quality reduction rate is less than 5%.

[1215] B: The quality reduction rate is between 5% and 7.5%.

[1216] C: The quality reduction rate exceeds 7.5% but is less than 10%.

[1217] D: The quality reduction rate exceeds 10%.

[1218] [Evaluation of long-term reliability]

[1219] A copper thin film was sputtered onto a silicon substrate, and a copper wiring pattern was formed by photolithography using a known method. The composition described in Table 2 was then applied to the copper wiring pattern using a spin coater. After drying at 100°C for 5 minutes, the sample was calcined at 250°C for 1 hour to produce a test piece for reliability evaluation. The copper wiring pattern of this test piece is a line & space pattern consisting of 10 μm lines and 10 μm spaces, with a copper wiring thickness of 1 μm.

[1220] A voltage of 5V was applied to the copper terminals of this test piece, and its conduction status was evaluated after 100 hours.

[1221] -Evaluation Criteria-

[1222] 4: Among the 10 test pieces put into the test, there were no poor conductivity.

[1223] 3: Of the 10 test pieces put into the test, 1 piece had poor conductivity.

[1224] 2: Of the 10 test pieces put into the test, 2 to 3 pieces had poor conductivity.

[1225] 1: Of the 10 test pieces put into the test, more than 4 pieces had poor conductivity.

[1226] [Table 5]

[1227]

[1228] Symbol Explanation

[1229] 10-Laminated structure, 12-Sealing layer, 14-Rewiring layer A, 16-Rewiring layer B, 18-Component with circuitry, 20-Circuit, 22-Semiconductor component, 24-Sealing material, 26-Conductive through-hole, 28-Connector A, 30-Connector B, 32-Other functional die, 34-Circuit component, 50-Laminated structure, 62-Carrier wafer, 64-Second carrier wafer, 66-Third carrier wafer, 102-Connector A, 104-Insulating pattern A, 106-Barrier layer, 108-Conductive pattern A, 110-Solder component, 112-Pillar.

Claims

1. A laminated body, comprising: A sealing layer, which includes components with circuitry and sealing material; Rewiring layer A, which contacts one side of the sealing layer and is connected to the circuit of the component; and The next wiring layer, B, contacts the other side of the sealing layer but is not directly connected to the circuitry of the component. The rewiring layer A and the rewiring layer B are configured to be electrically connected to other components. The rewiring layer A includes an insulating pattern A and a conductive pattern A existing between patterns of the insulating pattern A. The rewiring layer B includes an insulating pattern B and a conductive pattern B existing between patterns of the insulating pattern B. The insulating pattern A is composed of a composition that, when cured at 230°C for 3 hours, results in a cured product with a mass reduction rate of less than 10% when held at 250°C for 1 hour.

2. The laminated body according to claim 1, wherein, The component with circuitry is a functional chip.

3. The laminate according to claim 2, further comprising functional grains electrically connected to the redistribution layer A.

4. The laminated body according to claim 1, wherein, The component with circuitry is a wiring layer, and the stack also includes two or more semiconductor devices electrically connected to the rewiring layer A.

5. The laminate according to any one of claims 1 to 4, further comprising a circuit component including wiring and an insulating layer, the circuit component being connected to the rewiring layer B.

6. The laminate according to any one of claims 1 to 4, wherein, The rewiring layer A and rewiring layer B are connected via wiring.

7. The laminate according to any one of claims 1 to 4, wherein, The rewiring layer A comprises two or more layers consisting of the insulating pattern A and the conductive pattern A.

8. The laminate according to any one of claims 1 to 4, wherein, The conductive pattern A includes a line pattern, and the minimum line width of the line pattern is 0.1 μm to 10 μm.

9. The laminate according to any one of claims 1 to 4, wherein, The thickness of the rewiring layer A is 1 μm to 100 μm.

10. The laminate according to any one of claims 1 to 4, wherein at least a portion of the conductive pattern A has a barrier layer.

11. The laminate according to any one of claims 1 to 4, wherein the side of the rewiring layer A that is different from the side that contacts the sealing layer further includes a connecting member A.

12. The laminate according to claim 11, wherein, The connecting component A is roughly spherical in shape.

13. The laminate according to claim 12, wherein, The height of the connecting component A is less than 50 μm.

14. The laminate according to claim 11, wherein, The connecting component A is roughly cylindrical.

15. The laminate according to claim 14, wherein, The height of the connecting component A is less than 20 μm.

16. The laminate according to claim 11, wherein, The connecting component A includes a bonding pad structure with an average diameter of less than 5 μm.

17. A method for manufacturing a laminate, comprising: In the sealing layer forming process, a component with circuitry is embedded in a sealing material to form a sealing layer in which the circuitry of the component is exposed on one side and not exposed on the other side. In the process of forming rewiring layer A, a rewiring layer A comprising an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A is formed on the surface of the sealing layer exposing the circuit; and In the rewiring layer B forming process, a rewiring layer B comprising an insulating pattern B and a conductive pattern B existing between the patterns of the insulating pattern B is formed on the surface of the sealing layer that does not expose the circuit. The mass reduction rate of the insulating pattern A when it is kept at 250°C for 1 hour is less than 10%.

18. The method for manufacturing a laminate according to claim 17, wherein, The component with circuitry is a functional chip.

19. The method for manufacturing a laminate according to claim 17, wherein, The component with circuitry is a wiring layer, and the manufacturing method of the stack further includes a step of bonding the rewiring layer A to two or more functional grains.

20. The method for manufacturing a laminate according to claim 17, wherein, The process of forming the rewiring layer A includes the step of applying a composition for forming the insulating pattern A onto a sealing material to form a film.

21. The method for manufacturing a laminate according to claim 20, wherein, The composition for forming the insulating pattern A contains a resin having at least one repeating unit selected from the group consisting of repeating units represented by formula (2) and repeating units represented by formula (4). [Chemical Formula 1] In equation (2), A 1 and A 2 Each 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 Each can independently represent a hydrogen atom or a monovalent organic group, R z Represents a hydrogen atom or a monovalent organic group. [Chemical Formula 2] In equation (4), R 131 R represents a divalent organic group. 132 It represents a tetravalent organic group.

22. The method for manufacturing a laminate according to claim 20 or 21, wherein, The composition for forming the insulating pattern A contains at least one solvent selected from γ-butyrolactone, dimethyl sulfoxide, and N-methyl-2-pyrrolidone.

23. The method for manufacturing a laminate according to claim 20 or 21, wherein, The composition for forming the insulating pattern A also contains a polymeric compound.

24. The method for manufacturing a laminate according to claim 23, wherein, The polymerizable compounds include compounds having two or more olefinic unsaturated bonds.

25. The method for manufacturing a laminate according to claim 20 or 21, wherein, The composition for forming the insulating pattern A also contains a photopolymerization initiator.

26. The method for manufacturing a laminate according to claim 25, wherein, The photopolymerization initiator contains an oxime compound.

Images