Semiconductor package and method of manufacturing the same

Abstract

A semiconductor package and a method of manufacturing the same, the semiconductor package having: a sealing layer including at least one semiconductor die and a sealing material; a rewiring layer A in contact with at least one of the semiconductor dies and connected to a circuit of the semiconductor dies; a conductive connection part connected to the rewiring layer A; and a substrate connected to the conductive connection part, in which the rewiring layer A is formed by laminating layers including an insulating pattern A and a conductive pattern A present between the insulating pattern A, the insulating pattern A has a through-hole structure, and an angle formed by a side surface of the through-hole structure and a bottom surface of the insulating pattern A is 70-110 DEG.

Description

Technical Field

[0001] This invention relates to a semiconductor package and a method for manufacturing a semiconductor package. 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 for 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] Patent Document 2 describes a semiconductor package comprising a first rewiring layer, a second rewiring layer, a first semiconductor die, and a second semiconductor die. The first rewiring layer includes a first surface and a second surface opposite to the first surface. The second rewiring layer is disposed on the first surface of the first rewiring layer. The first semiconductor die is disposed on and electrically connected to the first and second rewiring layers. The second semiconductor die is disposed on and electrically connected to the second rewiring layer.

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: U.S. Patent Application Publication No. 2023 / 0089795

[0009] Patent Document 2: U.S. Patent Application Publication No. 2021 / 0035908 Summary of the Invention

[0010] The technical problem to be solved by the invention

[0011] In semiconductor packages using rewiring layers, it is required to suppress crack formation during long-term heat and humidity tests.

[0012] The purpose of this invention is to provide a semiconductor package that suppresses abnormalities such as cracks, peeling, and voids during long-term heat resistance and humidity resistance tests, as well as a method for manufacturing the above-mentioned semiconductor package.

[0013] means for solving technical problems

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

[0015] <1> A semiconductor package having:

[0016] A sealing layer comprising at least one semiconductor die and a sealing material;

[0017] A rewiring layer A is in contact with at least one of the aforementioned semiconductor chips and is connected to the circuit of the aforementioned semiconductor chip.

[0018] A conductive connection portion, which is connected to the aforementioned redistribution layer A; and

[0019] A substrate, which is connected to the aforementioned conductive connection portion.

[0020] The aforementioned rewiring layer A is formed by laminating layers comprising an insulating pattern A and conductive patterns A existing between the patterns of the insulating pattern A.

[0021] The aforementioned insulating pattern A has a through-hole structure, and the angle between the side surface of the through-hole structure and the bottom surface of the insulating pattern A is 70° to 110°.

[0022] <2> According to the semiconductor package described in <1>, wherein,

[0023] The aforementioned sealing layer comprises two or more semiconductor chips and sealing material, and the circuits of two or more of the aforementioned two or more semiconductor chips are connected to the aforementioned redistribution layer A.

[0024] <3> The semiconductor package according to <1> or <2> further has one or more semiconductor grains connected to the above-mentioned redistribution layer A, the semiconductor grains being located outside the above-mentioned sealing layer.

[0025] <4> The semiconductor package according to any one of <1> to <3>, wherein the redistribution layer A comprises a stacked structure of four or more layers.

[0026] <5> The semiconductor package according to any one of <1> to <4>, wherein the wiring in the redistribution layer A comprises a line pattern, the minimum line width of the line pattern being 0.1 to 10 μm.

[0027] <6> The semiconductor package according to any one of <1> to <5>, wherein the insulating pattern A comprises a resin having repeating units represented by the following formula (1-1).

[0028] [Chemical Formula 1]

[0029]

[0030] In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 This refers to an organic group that has 4 or more carbon atoms.

[0031] <7> According to the semiconductor package described in <6>, wherein,

[0032] X in equation (1-1) 1 and Y 1 Each is an organic group that independently contains a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4).

[0033] [Chemical Formula 2]

[0034]

[0035] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0036] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0037] <8> The semiconductor package according to any one of <1> to <7>, wherein the breaking elongation of the insulating pattern A is 40% or more.

[0038] <9> The semiconductor package according to any one of <1> to <8>, wherein the glass transition temperature of the insulating pattern A is 220°C or higher.

[0039] <10> A semiconductor package according to any one of <1> to <9>, wherein,

[0040] The Young's modulus of the aforementioned insulating pattern A is above 2.7 GPa.

[0041] <11> A method for manufacturing a semiconductor package, comprising:

[0042] In the sealing layer forming process, a semiconductor die is embedded in a sealing material to form a sealing layer in which a circuit with the semiconductor die exposed on one side and a circuit with the semiconductor die not exposed on the other side.

[0043] In the process of forming the rewiring layer A, a layer including an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A is stacked on the surface of the sealing layer that exposes the circuit to form the rewiring layer A.

[0044] In the connection forming process, a conductive connection is formed on a surface of the rewiring layer A that is different from the surface that contacts the sealing layer; and

[0045] The process of connecting the aforementioned connecting part to the substrate.

[0046] The above-mentioned rewiring layer A forming process includes a process of forming a through-hole structure using the above-mentioned insulating pattern A, wherein the angle between the side surface of the through-hole structure and the bottom surface of the insulating pattern A is 70 to 110°.

[0047] <12> According to the semiconductor packaging manufacturing method described in <11>, wherein,

[0048] The aforementioned insulating pattern A is formed using a negative photosensitive resin composition.

[0049] <13> The semiconductor packaging manufacturing method according to <12>, wherein,

[0050] The above-mentioned negative photosensitive resin composition contains a resin having at least one repeating unit selected from repeating units represented by formula (4-1) and repeating units represented by formula (4-2).

[0051] [Chemical Formula 3]

[0052]

[0053] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each can be independently a hydrogen atom or a monovalent organic group.

[0054] [Chemical Formula 4]

[0055]

[0056] In equation (4-2), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of the two groups independently represents a structure containing polymeric groups, and n and m independently represent integers from 0 to 4.

[0057] <14> The semiconductor packaging manufacturing method according to <13>, wherein,

[0058] In the above formula (4-1), X 1 and Y 1 Each is an organic group that independently contains a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4), wherein X in formula (4-2) above 1 and Y 1 Each is an organic group that independently contains a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4).

[0059] [Chemical Formula 5]

[0060]

[0061] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0062] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0063] <15> A method for manufacturing a semiconductor package according to any one of <12> to <14>, wherein,

[0064] The above-mentioned negative photosensitive resin composition contains an oxime initiator.

[0065] <16> A method for manufacturing a semiconductor package according to any one of <12> to <15>, wherein,

[0066] The above-mentioned negative photosensitive resin composition contains a polymeric compound having two or more olefinic unsaturated bonds.

[0067] <17> A method for manufacturing a semiconductor package according to any one of <12> to <16>, wherein,

[0068] In the above-mentioned rewiring layer A formation process, the photosensitive film formed from the above-mentioned negative photosensitive resin composition is exposed using an i-ray stepper.

[0069] <18> The semiconductor packaging manufacturing method according to <17>, wherein,

[0070] The numerical aperture of the aforementioned i-ray stepper is 0.10 to 0.60.

[0071] <19> A method for manufacturing a semiconductor package according to <17> or <18>, wherein,

[0072] The exposure illuminance of the aforementioned i-ray stepper is 500–50000 W / m². 2 .

[0073] <20> A method for manufacturing a semiconductor package according to any one of <17> to <19>, wherein,

[0074] The exposure dose using the aforementioned i-ray stepper is 1–2000 mJ / cm². 2 .

[0075] <21> A method for manufacturing a semiconductor package according to any one of <11> to <20>, wherein,

[0076] The above-mentioned through-hole structure is formed by using a solvent as a developing solution.

[0077] Invention Effects

[0078] According to the present invention, a semiconductor package that suppresses the generation of abnormalities such as cracks, peeling, and voids during long-term heat resistance and humidity resistance tests, and a method for manufacturing the above-mentioned semiconductor package are provided. Attached Figure Description

[0079] Figure 1 This is a schematic cross-sectional view showing an example of rewiring layer A.

[0080] Figure 2 It is magnification Figure 1 The diagram of the single-dot dashed section.

[0081] Figure 3 This is a schematic cross-sectional view showing a specific example of a conductive connection.

[0082] Figure 4 This is a schematic cross-sectional view illustrating an example of a semiconductor package of the present invention.

[0083] Figure 5 This is a schematic cross-sectional view illustrating another example of the semiconductor package of the present invention.

[0084] Figure 6 This is a schematic cross-sectional view illustrating an example of a semiconductor package manufacturing method according to the present invention.

[0085] Figure 7 This is a schematic cross-sectional view illustrating another example of a method for manufacturing a semiconductor package according to the present invention.

[0086] Figure 8 This is a schematic cross-sectional view showing the structure of the laminate used in the embodiments. Detailed Implementation

[0087] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0088] 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.

[0089] 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.

[0090] 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).

[0091] 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.

[0092] 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.

[0093] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] In this specification, the preferred combination of methods is a more preferred method.

[0100] (Semiconductor packaging)

[0101] The semiconductor package of the present invention comprises: a sealing layer including at least one semiconductor die and a sealing material; a redistribution layer A that contacts at least one of the semiconductor dies and is circuitally connected to the semiconductor die; a conductive connection portion connected to the redistribution layer A; and a substrate connected to the conductive connection portion, wherein the redistribution layer A is formed by stacking layers including an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A, the insulating pattern A having a through-hole structure, and the angle between the side surface of the through-hole structure and the bottom surface of the insulating pattern A being 70° to 110°.

[0102] Hereinafter, the angle formed by the side surface of the above-mentioned through-hole structure and the bottom surface of the insulating pattern A will also be referred to as the "cone angle".

[0103] The semiconductor package of the present invention suppresses abnormalities such as cracks, peeling, and voids in long-term heat resistance and humidity resistance tests.

[0104] The mechanism by which these effects are achieved is not yet clear, but the following is a hypothesis.

[0105] Previously, through-hole structures were formed in the rewiring layer to connect adjacent layers. However, during long-term heat resistance and moisture resistance tests, cracks, peeling, voids, and other abnormalities sometimes occurred in the insulation pattern near the through-hole structure.

[0106] Regarding through-hole structures, for example, through-holes are formed by patterning an insulating material and filling the through-holes with a metal such as copper.

[0107] However, in cases where the resolution of the insulating pattern is low, the shape of the through-hole may sometimes become, for example, an inverted truncated cone, resulting in a smaller cone angle.

[0108] It is speculated that if the cone angle becomes so small, the stress will be concentrated at the intersection of the side of the through-hole structure and the bottom of the insulating pattern A due to the expansion of the insulating pattern A during long-term heat resistance and moisture resistance tests. Therefore, it is easy to produce abnormalities such as cracks, peeling, and pores.

[0109] It is speculated that, conversely, when the cone angle is too large, the stress is concentrated at the intersection of the side of the through-hole structure and the upper surface of the insulating pattern A, which is prone to abnormalities such as cracks, peeling, and porosity.

[0110] Therefore, the inventors have studied a structure with a cone angle of 70 to 110°. They believe that this structure suppresses stress concentration, thus reducing the likelihood of abnormalities such as cracks, peeling, and voids.

[0111] The semiconductor packaging of the present invention will now be described in detail.

[0112] <Sealing layer>

[0113] The sealing layer preferably comprises a sealing material and at least one semiconductor die, wherein the semiconductor die is embedded in the sealing material.

[0114] [Sealing material]

[0115] 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).

[0116] 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.

[0117] 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.

[0118] 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.

[0119] [Semiconductor grains]

[0120] In this invention, a semiconductor chip refers to a chip assembled with circuitry, and specifically refers to a chip that displays storage, logic, and other functions.

[0121] Semiconductor chips are preferably semiconductor chips. Semiconductor chips are obtained, for example, by forming circuit patterns on a substrate such as silicon and monolithically processing them.

[0122] As a semiconductor chip, it is not particularly limited, and examples include memory ICs, logic ICs, ASICs, and semiconductor chips that further integrate these.

[0123] The number of semiconductor chips sealed by the sealing layer is not particularly limited; it can be one or more. Here, the sealing layer is a sealing layer comprising two or more semiconductor chips and sealing material, and the connection of the circuits of two or more of the aforementioned two or more semiconductor chips to the aforementioned redistribution layer A is also one of the preferred embodiments of the present invention.

[0124] The size of semiconductor grains is not particularly limited; for example, semiconductor grains with one side being 100μm to 10cm can be cited.

[0125] Semiconductor chips can have conductive components that are connected to the circuitry within the semiconductor chip.

[0126] Examples of conductive components include conductive pads.

[0127] 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.

[0128] Preferably, the circuit or the conductive component in the semiconductor die is exposed on one side of the sealing layer, while on the other side, neither the circuit or the conductive component in the semiconductor die is exposed.

[0129] 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.

[0130] -Conductive Part-

[0131] 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.

[0132] The aforementioned conductive portion, for example, allows the rewiring layer A to be connected to other components.

[0133] The thickness of the sealing layer is not particularly limited and can be determined by taking into account factors such as the thickness of the semiconductor grains. For example, it is preferably 1 μm to 500 μm, and more preferably 10 μm to 200 μm.

[0134] <Rewiring Layer A>

[0135] The rewiring layer A is a layer that contacts at least one of the semiconductor chips and is connected to the circuit of the semiconductor chip, and is a layer formed by stacking layers including an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A.

[0136] Here, the conductive pattern A is connected to the semiconductor grains in the sealing layer.

[0137] For example, one preferred method is to bring at least a portion of the conductive pattern A into contact with a circuit in a semiconductor component exposed on one side of the sealing layer or a conductive component connected to the circuit.

[0138] [Insulation Pattern A]

[0139] The volume resistivity of insulating pattern A at 25°C is not particularly limited, but is preferably 1×10⁻⁶. 8 Ω·cm or higher, 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.

[0140] Insulating pattern A has a through-hole structure.

[0141] Through-hole structures are structures used to connect adjacent layers in the rewiring layer A, and are preferably generally cylindrical, generally polygonal, or similar structures.

[0142] The diameter of the through-hole structure (or the equivalent diameter of a circle when it is a polygonal column) is not particularly limited, but is preferably 1 to 20 μm, and more preferably 2 to 10 μm.

[0143] A conductive pattern A is preferably configured within the through-hole structure.

[0144] Furthermore, other layers, such as a seed layer for forming the conductive pattern A, can be further formed within the through-hole structure.

[0145] In the rewiring layer A, the angle (conical angle) formed by the side surface of the above-mentioned through-hole structure and the bottom surface of the insulating pattern A is 70 to 110°, preferably 75 to 105°, and more preferably 80 to 100°.

[0146] Here, when there is deformation on the side of the through hole structure, the aforementioned cone angle is set as the angle formed by the straight line connecting the endpoint of the bottom surface of the insulating pattern A and the endpoint of the exposed part on the upper surface side of the insulating pattern A, and the bottom surface of the insulating pattern A.

[0147] In this specification, the bottom surface refers to the surface closest to the sealing layer, and the top surface refers to the surface furthest from the sealing layer.

[0148] The cone angle is determined as follows: the semiconductor package is cut on the face including the center of the through-hole structure, the cross-section is ground by the ArBlade5000 milling machine (manufactured by Hitachi, Ltd.), and an SEM image is obtained using the FE-SEM SU-4800 (manufactured by Hitachi, Ltd.). The angle between the bottom surface of the insulating pattern A and the side surface of the insulating pattern A is then measured.

[0149] For details of the determination method, please refer to the examples described below.

[0150] The aforementioned cone angle can be adjusted according to the structure and content of the resin, polymeric compounds, etc. contained in the negative photosensitive resin composition described later, the numerical aperture of the exposure light when forming the insulating pattern A, the exposure amount, the exposure illuminance, the type of developer during development, etc.

[0151] The insulating pattern A preferably includes a resin, and more preferably includes a polyimide.

[0152] Furthermore, the insulating pattern A is preferably a cured product of the composition for forming the insulating pattern A, which will be described later.

[0153] The insulating pattern A preferably comprises a resin having repeating units represented by the following formula (1-1).

[0154] This resin, for example, is contained in the insulating pattern as a polyimide contained in the negative photosensitive resin composition described later, or as a polyimide formed by cyclization of a polyimide precursor contained in the negative photosensitive resin composition.

[0155] Here, in the insulating pattern, it is preferable to polymerize the polymerizable groups in the polyimide or polyimide precursor contained in the negative photosensitive resin composition described later.

[0156] [Chemical Formula 6]

[0157]

[0158] In equation (1-1), X 1 Y represents an organic group with 4 or more carbon atoms. 1 This refers to an organic group that has 4 or more carbon atoms.

[0159] X in equation (1-1) 1 and Y 1 The preferred method is the same as X in equation (4-2) described later. 1 and Y 1 The preferred method is the same.

[0160] Wherein, the preferred value is X in equation (1-1) 1 and Y 1 Each is an organic group that independently contains a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4).

[0161] [Chemical Formula 7]

[0162]

[0163] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0164] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0165] The preferred manner of the organic group containing the structure formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4) will be described later.

[0166] 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.

[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 negative photosensitive resin composition described later.

[0170] The glass transition temperature of the insulating pattern A is preferably 200°C or higher, more preferably 210°C or higher, and even more preferably 220°C or higher.

[0171] The upper limit of the glass transition temperature is not particularly limited; for example, it can be set to below 350°C.

[0172] 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.

[0173] (1) Increase the temperature from 25°C to 300°C at a rate of 10°C / minute.

[0174] (2) Cooling from 300℃ to 25℃

[0175] (3) Increase the temperature from 25℃ to 500℃ at a rate of 10℃ / minute.

[0176] (4) Cooling from 500℃ to 25℃

[0177] The glass transition temperature described above can be adjusted according to the structure and content of specific resins, polymeric compounds, etc. contained in the negative photosensitive resin composition described later.

[0178] The Young's modulus of insulating pattern A is preferably above 2.7 GPa.

[0179] The aforementioned Young's modulus is more preferably 2.8 GPa or higher, and even more preferably 3.0 GPa or higher. The upper limit of the aforementioned Young's modulus is not particularly limited, for example, it is preferably 10.0 GPa or lower.

[0180] For the determination of Young's modulus (modulus), refer to the method described in JIS-K6251:2017, and use a tensile testing machine (Tensilon) at a crosshead speed of 300 mm / min, 25°C, and 65%RH (relative humidity).

[0181] The coefficient of thermal expansion (CTE) of the insulating pattern A is preferably 0 to 80 ppm / K, more preferably 5 to 75 ppm / K, and even more preferably 10 to 70 ppm / K.

[0182] The coefficient of thermal expansion of insulating pattern A is determined by the following method.

[0183] 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.

[0184] The heating and cooling conditions during the evaluation are set as follows (1) to (4).

[0185] (1) Heat from room temperature to 130°C at a heating rate of 5°C / minute.

[0186] (2) Cool down from 130℃ to 10℃ at a cooling rate of 5℃ / minute.

[0187] (3) Heat from 10℃ to 220℃ at a heating rate of 5℃ / minute.

[0188] (4) Allow to cool naturally to room temperature.

[0189] 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.

[0190] [Conductive pattern A]

[0191] 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.

[0192] The preferred material for forming the conductive pattern A is a metal.

[0193] 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.

[0194] The conductive pattern A preferably includes a line and a space pattern. The line and space pattern includes, for example, a line and space pattern in which the conductive pattern A is a line portion and the insulating pattern A is a space portion.

[0195] When the conductive pattern A includes a line pattern, the minimum line width of the line pattern is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, and even more preferably 0.3 to 10 μm.

[0196] The conductive pattern A preferably has a barrier layer in at least a portion.

[0197] 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).

[0198] 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.

[0199] The components constituting the barrier layer are not particularly limited, but examples include tungsten, titanium, or alloys containing at least one of these metals.

[0200] 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.

[0201] [Structure of Re-wiring Layer A]

[0202] The rewiring layer A is formed to be electrically connected to the conductive connection portion described later.

[0203] 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.

[0204] For example, the exposed conductive pattern A or barrier layer is connected to the conductive connection portion described later, and then the wiring layer A is electrically connected to other components.

[0205] Furthermore, the rewiring layer A may include a conductive pad in the outermost layer (i.e., the layer furthest from the sealing layer).

[0206] Metal is preferred as the material for the conductive pad.

[0207] 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.

[0208] When a conductive pad is present, the conductive pattern A is electrically connected to other components via the conductive pad.

[0209] The rewiring layer A is a layer formed by stacking layers including an insulating pattern A and a conductive pattern A.

[0210] The rewiring layer A preferably comprises 1 to 20 layers consisting of an insulating pattern A and a conductive pattern A, and more preferably comprises 2 to 10 layers consisting of an insulating pattern A and a conductive pattern A.

[0211] 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.

[0212] The diagram illustrates an example of rewiring layer A.

[0213] Figure 1 This is a schematic cross-sectional view showing an example of rewiring layer A.

[0214] The rewiring layer A is formed to include an insulating pattern A12, a conductive pattern A14, and a conductive pad 16.

[0215] The conductive pattern A14 is connected to the semiconductor die included in the sealing layer in the exposed portion 18.

[0216] The conductive pad is further formed with conductive connections, which will be described later.

[0217] Here, the portion surrounded by the dashed line in the rewiring layer A corresponds to the via structure.

[0218] exist Figure 1 In the diagram, the rewiring layer A is temporarily described as a layer consisting of three layers, including an insulating pattern A and a conductive pattern A.

[0219] Figure 2 It is magnification Figure 1 The diagram of the single-dot dashed section.

[0220] exist Figure 2 In this context, θ is the angle (cone angle) between the side surface of the through-hole structure and the bottom surface of the insulating pattern A.

[0221] <Other Semiconductor Dies>

[0222] The semiconductor package of the present invention preferably also has one or more semiconductor dies connected to the redistribution layer A, the semiconductor dies being located outside the sealing layer.

[0223] The preferred configurations for other semiconductor chips are the same as those for semiconductor chips included in the aforementioned sealing layer, except that they are not sealed by the sealing layer.

[0224] Other semiconductor chips are preferably disposed, for example, on the side of the sealing layer opposite to the redistribution layer A and connected to the redistribution layer A through the aforementioned conductive portion.

[0225] When the semiconductor package of the present invention includes other semiconductor chips, the number of other semiconductor chips is one or more, preferably one to ten, and more preferably one to four.

[0226] In this approach, when more than two semiconductor grains are included, the semiconductor grains can be the same or different.

[0227] <Conductive connection>

[0228] The semiconductor package of the present invention further includes a conductive connection portion on the side of the rewiring layer that is different from the side that contacts the sealing layer.

[0229] The conductive connection portion is preferably any one of the following: a generally spherical or cylindrical bonding pad structure with an average diameter of 5 μm or less.

[0230] Furthermore, the semiconductor package of the present invention may include a barrier layer between the redistribution layer A and the conductive connection portion.

[0231] When the conductive connection is approximately spherical, the conductive connection is preferably a solder ball, a ball grid array (BGA) ball, or a C4 bump.

[0232] Figure 3 (a) is a schematic cross-sectional view when the conductive connection is roughly spherical.

[0233] exist Figure 3 In (a), the conductive connection portion 102 is connected to the conductive pattern A108 in the outermost layer of the redistribution layer A via the conductive pad 104. The conductive pattern A108 is formed between the insulating patterns A106 in the outermost layer of the redistribution layer A.

[0234] Here, a barrier layer can be formed between the conductive pad 104 and the conductive pattern A108.

[0235] When the conductive connection is generally spherical, the material constituting the conductive connection is not particularly limited, but Sn, Pb, Ag, Cu, Ni, Bi or an alloy containing any of these are preferred.

[0236] When the conductive connection portion is approximately spherical, the height of the conductive connection portion is preferably 50 μm or less, more preferably 20 to 50 μm, and even more preferably 20 to 40 μm.

[0237] When the conductive connection is generally columnar, the conductive connection is preferably a column with a solder component at the top.

[0238] Figure 3 (b) is a schematic cross-sectional view when the conductive connection is roughly columnar.

[0239] exist Figure 3 In (b), the conductive connection part 102 is a component consisting of solder part 110 and post 112.

[0240] exist Figure 3 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.

[0241] exist Figure 3 In (b), the conductive connection portion 102 is connected to the conductive pattern A108, which is formed between the insulating patterns A106.

[0242] When the conductive connection 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.

[0243] 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.

[0244] When the conductive connection is generally columnar, the height of the conductive connection is preferably less than 20 μm, more preferably 10 to 20 μm, and even more preferably 10 to 15 μm.

[0245] When the conductive connection is a bonding pad structure with an average diameter of 5 μm or less, the conductive connection is preferably formed to be height-aligned with the insulating pattern A, and the conductive connection and the insulating component are substantially flat.

[0246] Figure 3 (c) is a schematic cross-sectional view of a bonding pad structure with an average diameter of 5 μm or less for the conductive connection part.

[0247] exist Figure 3 In (c), the conductive connection portion 102 is connected to the conductive pattern A108, which is formed between the insulating patterns A106.

[0248] When the conductive connection portion 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.

[0249] When the conductive connection part 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.

[0250] 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.

[0251] <Substrate>

[0252] The semiconductor package of the present invention has a substrate connected to the above-described conductive connection portion.

[0253] The material used as a substrate is not particularly limited, and can include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe; paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; and electrode plates for plasma display panels (PDPs). Layers such as bonding layers or oxide layers formed from hexamethyldisilazane (HMDS) and sealing materials (epoxy molding compound: EMC) can be deposited on the surface of these substrates.

[0254] The substrate can be in the form of a wafer or a panel.

[0255] In this invention, semiconductor substrates are preferred, and silicon substrates (silicon wafers) are more preferred.

[0256] The substrate may have an electronic circuit region including electronic circuits. Furthermore, the electronic circuit may include components such as semiconductors. Preferably, the electronic circuit is electrically bonded to the conductive pattern A.

[0257] Furthermore, the substrate may have conductive components on a side different from the side connected to the conductive pattern A, for connecting to other components.

[0258] <Specific Examples of Semiconductor Packaging>

[0259] Hereinafter, examples of specific methods of semiconductor packaging according to the present invention will be illustrated in the figures, but the present invention is not limited to these.

[0260] Figure 4 This is a schematic cross-sectional view illustrating an example of a semiconductor package of the present invention.

[0261] exist Figure 4 In the semiconductor package 20, there are: a sealing layer 22, an insulating pattern A12, a redistribution layer A including a conductive pattern A14 and a conductive pad 16, a conductive connection portion 24, and a substrate 26.

[0262] exist Figure 4 In this drawing, the thickness of each layer has been appropriately varied to facilitate verification. In practice, for example, the thickness of the rewiring layer A relative to the sealing layer 22 may be several tens to several hundredths, and sometimes differs from the actual dimensions. This is also true in other drawings.

[0263] The sealing layer 22 comprises two semiconductor chips 28 and a sealing material 30.

[0264] Semiconductor die 28 is connected to conductive pattern A14 in redistribution layer A.

[0265] Furthermore, in Figure 4 In this configuration, a conductive connection portion 24 is formed on the side of the rewiring layer A opposite to the sealing layer 22. Figure 4 In the text, the conductive connection portion 24 is described as being roughly spherical, but as described above, it can be other shapes such as roughly cylindrical or bonding pad.

[0266] exist Figure 4 In this configuration, conductive connection portion 24 is connected to substrate 26. Electrode 32 and other conductive connection portions 34 for connecting to other components are disposed on the side of substrate 26 opposite to conductive connection portion 24. The space between substrate 26 and redistribution layer A can be filled with a known underfill material.

[0267] Figure 5 This is a schematic cross-sectional view illustrating another example of the semiconductor package of the present invention.

[0268] Figure 5 Among the components marked with various symbols, those marked with... Figure 4 The components of the same symbol in the text are those that are identical to the symbol in the text. Figure 4 The same component as the one in the picture.

[0269] exist Figure 5 In the semiconductor package 20, the sealing layer 22 includes only one semiconductor die 28, and a conductive pattern A14 and two other semiconductor dies 38 are connected via conductive through-holes 36 formed in the sealing layer 22, other conductive pads 40, and other conductive connections 42. Here, an insulating layer 44 is formed between the sealing layer 22 and the other conductive pads 40.

[0270] Here, the space between the redistribution layer A and the substrate 26 can be filled with a known underfill material.

[0271] Furthermore, the space between the insulating layer 44 and the sealing layer 22 can be filled with a known bottom filler material.

[0272] Furthermore, the semiconductor die 38 can be sealed with a known sealing material.

[0273] Semiconductor packaging manufacturing methods

[0274] The semiconductor package manufacturing method of the present invention includes: a sealing layer forming step, wherein a semiconductor die is embedded in a sealing material to form a sealing layer having a circuit exposed on one side of the semiconductor die and a circuit not exposed on the other side; a rewiring layer A forming step, wherein a layer comprising an insulating pattern A and a conductive pattern A existing between patterns of the insulating pattern A is stacked on the side of the sealing layer exposing the circuit to form a rewiring layer A; a connection forming step, wherein a conductive connection is formed on the side of the rewiring layer A that is different from the side that contacts the sealing layer; and a step of connecting the connection to a substrate, wherein the rewiring layer A forming step includes a step of forming a through-hole structure using the insulating pattern A, wherein the angle between the side surface of the through-hole structure and the bottom surface of the insulating pattern A is 70 to 110°.

[0275] According to the semiconductor package manufacturing method of the present invention, the semiconductor package of the present invention described above can be obtained. That is, a semiconductor package that suppresses the formation of abnormalities such as cracks, peeling, and voids during long-term heat resistance and humidity resistance tests can be obtained.

[0276] <Sealing layer formation process>

[0277] The semiconductor package manufacturing method of the present invention includes a sealing layer formation process.

[0278] Through the sealing layer forming process, a sealing layer comprising a sealing material and a semiconductor die embedded in the sealing material can be obtained. The sealing layer exposes the circuit of the semiconductor die on one side and does not expose the circuit of the component on the other side.

[0279] The sealing layer formation process can be performed, for example, by disposing the semiconductor grains on a carrier wafer (pre-support) and applying the curable composition to embed the semiconductor grains to cure the curable composition.

[0280] Furthermore, a known pre-bonding layer can also be formed on the carrier wafer.

[0281] For the application and solidification of these, well-known methods can be referenced.

[0282] The preferred embodiments of the curable composition and the semiconductor grains are as described above.

[0283] Furthermore, during the sealing layer formation process, the surface can also be ground after the sealing material has cured.

[0284] Examples of the aforementioned grinding methods include chemical mechanical polishing (CMP) and physical polishing, but are not limited to these.

[0285] For example, on the side of a circuit with semiconductor chips, the circuit with semiconductor chips can be exposed on the surface of the sealing layer by grinding the cured sealing material.

[0286] 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.

[0287] Furthermore, the circuit can be exposed from the sealing layer by not grinding during the sealing layer formation process, but simply by not sealing the surface of the circuit on which the semiconductor die is disposed.

[0288] 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 semiconductor package of the present invention described above.

[0289] The conductive portion may not be formed during the sealing layer forming process, as will be described later, or it may be formed after the rewiring layer A forming process.

[0290] <Passivation layer formation process>

[0291] The semiconductor package manufacturing method of the present invention may further include a passivation layer forming process after the sealing layer forming process.

[0292] The passivation layer formation process is preferably performed after the sealing layer formation process and before the rewiring layer A formation process.

[0293] A passivation layer is formed by coating a passivation film onto the surface of a semiconductor grain. By forming a passivation layer, the influence of external gases on the semiconductor grain, the adhesion of dust, and contamination caused by water or metal can sometimes be suppressed.

[0294] 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.

[0295] 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).

[0296] <Re-wiring layer A formation process>

[0297] The semiconductor package manufacturing method 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.

[0298] The rewiring layer A is formed on the surface of the sealing material that exposes the circuit through 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 semiconductor package of the present invention described above.

[0299] The rewiring layer A forming process preferably includes the step of applying a negative photosensitive resin composition onto the sealing layer to form a film (film forming process).

[0300] That is, a negative photosensitive resin composition is preferably used to form the insulating pattern A in the redistribution layer A.

[0301] 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.

[0302] 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.

[0303] The following is a detailed description of each process step. Furthermore, details regarding the negative photosensitive resin composition (hereinafter also referred to as the "composition") will be discussed later.

[0304] <Membrane Formation Process>

[0305] 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.

[0306] As a method for applying the composition to the sealing layer, coating is preferred.

[0307] 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.

[0308] 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 a sealing layer.

[0309] 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.

[0310] 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.

[0311] 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.

[0312] <Drying Process>

[0313] 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).

[0314] That is, the rewire layer A forming process may include a drying process for drying the film formed by the film forming process.

[0315] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0316] 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.

[0317] <Exposure Process>

[0318] The above-mentioned film can be used in an exposure process for selectively exposing the film.

[0319] The rewire layer A formation process may include an exposure process that selectively exposes the film formed by the film formation process.

[0320] 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.

[0321] 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 .

[0322] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0323] 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, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. 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.

[0324] 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.

[0325] Here, in the process of forming the rewiring layer A, it is preferable to expose the photosensitive film formed from the above-mentioned negative photosensitive resin composition using an i-ray stepper.

[0326] The cone angle can be adjusted by appropriately adjusting the numerical aperture, exposure illuminance, and exposure amount of the i-ray stepper.

[0327] The numerical aperture of the i-ray stepper is preferably 0.10 to 0.60.

[0328] When high resolution is required, a high numerical aperture is preferred; when a wide focal margin is required, a low numerical aperture is preferred.

[0329] The preferred high numerical aperture is 0.40 to 0.60, more preferably 0.45 to 0.57, and even more preferably 0.47 to 0.55.

[0330] As a low numerical aperture, it is preferably 0.10 to 0.30, more preferably 0.13 to 0.27, and even more preferably 0.15 to 0.25.

[0331] The preferred exposure illuminance for an I-ray stepper is 500–50000 W / m². 2 More preferably, it is 1000–30000 W / m 2 Further preferred is 3000~20000W / m 2 .

[0332] The optimal exposure dose using an i-ray stepper is 1–2000 mJ / cm². 2 More preferably, it is 50–1500 mJ / cm². 2 More preferably, it is 100–700 mJ / cm 2 .

[0333] <Post-exposure heating process>

[0334] The above-mentioned film can be used in a process of heating after exposure (post-exposure heating process).

[0335] 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.

[0336] The post-exposure heating process can be performed after the exposure process and before the development process.

[0337] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0338] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0339] 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.

[0340] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0341] The heating method used in the post-exposure heating process is not particularly limited and can use known hot plates, ovens, infrared heaters, etc.

[0342] 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.

[0343] <Developing Process>

[0344] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0345] 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.

[0346] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0347] 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.

[0348] Here, regarding the through-hole structure in the insulating pattern A, it is preferable to form the through-hole structure by using a solvent as a developing solution.

[0349] [Developing solution]

[0350] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0351] 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.

[0352] 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.

[0353] 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.

[0354] 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.

[0355] 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.

[0356] 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.

[0357] 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.

[0358] 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.

[0359] 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.

[0360] 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.

[0361] 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.

[0362] The developer may contain only one type of alkaline compound or two or more types of alkaline compounds.

[0363] 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.

[0364] 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.

[0365] 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.

[0366] 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.

[0367] 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.

[0368] Developer solutions may also contain other ingredients.

[0369] Other components include, for example, well-known surfactants or well-known defoamers.

[0370] [Method for supplying developer]

[0371] 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.

[0372] 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.

[0373] 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.

[0374] 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.

[0375] 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.

[0376] 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.

[0377] [Rinse solution]

[0378] 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.

[0379] 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.

[0380] 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.

[0381] 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.

[0382] 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.

[0383] The rinsing solution may contain at least one of an alkaline compound and an alkali-generating agent.

[0384] 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.

[0385] 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.

[0386] 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.

[0387] 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.

[0388] 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.

[0389] 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.

[0390] The rinsing solution may also contain other ingredients.

[0391] Other components include, for example, well-known surfactants or well-known defoamers.

[0392] [Method for supplying flushing fluid]

[0393] 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.

[0394] 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.

[0395] 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.

[0396] 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.

[0397] 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.

[0398] 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.

[0399] 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.

[0400] 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.

[0401] 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.

[0402] 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.

[0403] 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.

[0404] 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.

[0405] <Heating Process>

[0406] 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.

[0407] That is, the process of forming the rewire layer A may include a heating process that heats the pattern obtained by the developing process.

[0408] During the heating process, resins such as polyimide precursors are cyclized to become resins such as polyimide.

[0409] Furthermore, crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed.

[0410] 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.

[0411] 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.

[0412] 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.

[0413] 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.

[0414] 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.

[0415] 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.

[0416] 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.

[0417] 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.

[0418] 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.

[0419] Furthermore, cooling can be performed after heating, and the preferred cooling rate at this time is 1 to 5°C / minute.

[0420] 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.

[0421] 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.

[0422] <Post-development exposure process>

[0423] 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.

[0424] 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.

[0425] 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.

[0426] 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.

[0427] 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 .

[0428] Regarding the post-development exposure process, for example, the light source used in the above-mentioned exposure process can be used, preferably broadband light.

[0429] <Metal Layer Formation Process>

[0430] 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.

[0431] 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.

[0432] 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).

[0433] 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.

[0434] 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.

[0435] 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.

[0436] 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.

[0437] <Resist layer formation process, resist layer stripping process>

[0438] 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.

[0439] Furthermore, the process of forming the rewiring layer A can include a resist layer stripping process after the metal layer formation process.

[0440] These processes can be carried out using known methods.

[0441] By performing these processes, it is also possible to form lines and spatial patterns as conductive patterns A.

[0442] <Grinding Process>

[0443] 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.

[0444] 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.

[0445] <Layering Process>

[0446] The rewiring layer A forming process of the present invention includes a lamination process.

[0447] 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.

[0448] 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.

[0449] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0450] 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.

[0451] The composition, shape, and film thickness of the above layers can be the same or different.

[0452] 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.

[0453] <Surface activation treatment process>

[0454] 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.

[0455] 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) and after the surface activation treatment process of the composition layer.

[0456] 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.

[0457] 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.

[0458] 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.

[0459] <Connector Pad Forming Process>

[0460] 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.

[0461] 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 resist layer as needed, forming a bonding pad by plating, and then peeling off the resist layer.

[0462] <Carrier wafer bonding process, carrier wafer peeling process>

[0463] The semiconductor package manufacturing method of the present invention can include: a carrier wafer bonding process for bonding a carrier wafer to the semiconductor package being manufactured, and a carrier wafer peeling process for peeling off the bonded carrier wafer.

[0464] For example, in the case where a carrier wafer is bonded to a semiconductor die in the sealing layer formation process to form a sealing layer, and a rewiring layer A is formed on the sealing layer in the rewiring layer formation process, in order to bond other semiconductor dies, 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, thereby also being able to reverse the surface of the carrier wafer.

[0465] The carrier wafer peeling process and the carrier wafer bonding process can be carried out by known methods.

[0466] Furthermore, known carrier chips can be used without special restrictions as carrier chips.

[0467] <Conductive component forming process>

[0468] The method for manufacturing semiconductor chips of the present invention may further include a conductive portion forming step for forming the above-mentioned conductive portion.

[0469] The conductive part forming process can be performed, for example, between the sealing layer forming process and the rewiring layer A forming process, or after the rewiring layer A forming process.

[0470] 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.

[0471] The holes mentioned above can be through holes or non-through holes.

[0472] Furthermore, in the formation of the aforementioned holes, residues such as the sealing layer generated during processing can be removed by known desmearing treatments.

[0473] As a method for forming conductive parts, methods known in the art can be used without particular restriction.

[0474] <Inspection Procedure>

[0475] After the formation process of the rewiring layer A, there may also be an inspection process to check the surface shape, conductivity, insulation, and presence or absence of voids of the formed rewiring layer A.

[0476] As a method for inspection procedures, methods known in the art can be used without particular restriction.

[0477] <Connection Forming Process>

[0478] The semiconductor package manufacturing method of the present invention further includes a connection forming step in which a conductive connection portion is formed on a surface of the redistribution layer A that is different from the surface that contacts the sealing layer.

[0479] The preferred embodiment of the conductive connection portion is the same as the preferred embodiment of the conductive connection portion of the semiconductor package of the present invention.

[0480] As a method for forming conductive connections, methods known in the art can be used without particular limitation.

[0481] <Other Semiconductor Die Bonding Processes>

[0482] The semiconductor package manufacturing method of the present invention may further include a step of bonding other semiconductor dies to the surface of the above-mentioned redistribution layer A that is different from the surface that contacts the above-mentioned sealing layer.

[0483] Other semiconductor chips are preferably connected to the redistribution layer A via the aforementioned conductive portion formed within the sealing layer.

[0484] The preferred methods for other semiconductor chips are the same as the preferred methods for other semiconductor chips in the semiconductor package of the present invention.

[0485] When bonding other semiconductor chips, at least one of heating and pressurization can be performed. As a method for bonding other semiconductor chips, methods known in the art can be used without particular limitation.

[0486] <Substrate bonding process>

[0487] The semiconductor package manufacturing method of the present invention includes a step of joining the conductive connection portion to the substrate.

[0488] The substrate is preferably connected to the redistribution layer A via a conductive connection portion.

[0489] The preferred method for the substrate is the same as the preferred method for the substrate of the semiconductor die of the present invention.

[0490] When bonding substrates, at least one of heating and pressurization can be performed. As a bonding method for substrates, methods known in the art can be used without particular limitation.

[0491] <Other Processes>

[0492] The semiconductor package manufacturing method of the present invention may also include other steps.

[0493] Other processes include cleaning components as needed after each process, forming other rewiring layers on the side of the sealing layer opposite to rewiring layer A, and forming other connections on the side of the sealing layer opposite to rewiring layer A.

[0494] The process for forming other rewiring layers is not particularly limited, and the process for forming known rewiring layers can be used. However, for example, except that the cone angle is not limited, it can be carried out by the same method as the process for forming rewiring layer A described above.

[0495] The process for forming other connecting parts is not particularly limited, and the process for forming known connecting parts can be used, but for example, it can be carried out by the same method as the connecting part forming process described above.

[0496] Figure 6 This is a schematic cross-sectional view illustrating an example of a semiconductor package manufacturing method according to the present invention.

[0497] exist Figure 6 In (a), a layer 46 formed of a curable resin composition is formed on a carrier wafer 62, and two semiconductor grains 28 are disposed on the layer 46 formed of the curable resin composition. Details of the curable resin composition are as described above. Here, the layer 46 formed of the curable resin composition can be cured or can be left uncured.

[0498] Figure 6 (b) indicates that the semiconductor die 28 is embedded in the sealing material 30. Figure 6 (a) shows the state in the laminate. The surface of the semiconductor die 28 is exposed. The sealing material 30 is formed, for example, by applying the above-described curable resin composition in a manner that embeds the semiconductor die and then curing it. Here, the surface of the semiconductor die 28 can be exposed by a polishing process, or it can be exposed by filling it with the sealing material 30.

[0499] Figure 6 (c) is for the reason that Figure 6 (b) is a schematic cross-sectional view showing the state of the laminate forming a layer comprising an insulating pattern A12 and a conductive pattern A14.

[0500] For example, firstly, after forming the insulating pattern A12 through the aforementioned film formation process, exposure process, development process, and heating process, the conductive pattern A14 is formed through the aforementioned metal layer formation process, thereby obtaining... Figure 6 The layered structure described in (c).

[0501] Here, the insulating pattern A12 includes a through-hole structure, and the conductive pattern A14 is included as a through-hole pattern.

[0502] In this invention, by appropriately setting the composition of the negative photosensitive resin composition used to form the insulating pattern A12, the exposure illuminance and exposure amount in the exposure process, the numerical aperture of the stepper, the development conditions in the development process, the developer, etc., the cone angle in the through-hole structure of the insulating pattern A12 can be adjusted to 70 to 110°.

[0503] Figure 6 (d) is... Figure 6(c) is a schematic cross-sectional view of the laminate shown, which further forms a layer including an insulating pattern A12 and a conductive pattern A14.

[0504] For example, through the above-mentioned film formation process, exposure process, development process, and heating process, the film is... Figure 6 After the laminate shown in (c) forms the insulating pattern A12, the conductive pattern A14 is formed through the metal layer forming process described above, thereby obtaining... Figure 6 The layered structure described in (d). Here, in Figure 6 The newly formed conductive pattern A14 in (d) can be configured as, for example, a pattern including lines and spatial patterns.

[0505] Figure 6 (e) is for Figure 6 (d) is a schematic cross-sectional view of the state in which a conductive pad 16 is formed on the basis of a layer comprising an insulating pattern A12 and a conductive pattern A14.

[0506] Thus, by stacking insulating pattern A12 and conductive pattern A14, and forming conductive pad 16 as needed, a redistribution layer A can be formed.

[0507] After that, Figure 6 (e) The laminate shown undergoes a connection formation process and a substrate bonding process, and the carrier wafer 62 is peeled off, thereby obtaining Figure 4 The semiconductor packaging described in the document.

[0508] Figure 7 This is a schematic cross-sectional view illustrating an example of a semiconductor package manufacturing method according to the present invention.

[0509] exist Figure 7 In (a), a sealing layer having a semiconductor die 28 embedded in a sealing material 30 is formed on the carrier wafer 62, and a redistribution layer A including an insulating pattern A12, a conductive pattern A14 and a conductive pad 16 is formed on the surface of the sealing layer that exposes the semiconductor die 28.

[0510] Figure 7 The laminate shown in (a) can be connected with the above-mentioned Figure 6 The same method is used to obtain the laminate shown.

[0511] Figure 7 (b) is in Figure 7 (a) is a schematic cross-sectional view of the laminate in which conductive through-holes 36, insulating layers 44, and other conductive pads 40 are formed.

[0512] Figure 7(b) The laminate shown is obtained by bonding the second carrier wafer 64 to the side of the redistribution layer A opposite to the sealing layer, peeling off the carrier wafer 62, and forming an insulating layer 44 on the side of the sealing layer opposite to the side where the redistribution layer A is formed, forming a conductive through hole 36 and forming other conductive pads 40 through a conductive part forming process.

[0513] Figure 7 (c) is correct Figure 7 (b) is a schematic cross-sectional view of the state in which the laminate forms other conductive pads 40 and is bonded to other semiconductor grains 38.

[0514] Afterwards, through from Figure 7 (c) The second carrier wafer 64 is peeled off from the laminate shown, and the third carrier wafer is bonded to other semiconductor wafers 38 as needed. A connection formation process and a substrate bonding process are performed on the redistribution layer A, and the third carrier wafer is peeled off as needed. This allows for the acquisition of... Figure 5 The semiconductor packaging described in the document.

[0515] The following is a detailed description of the negative photosensitive resin composition (the composition).

[0516] As a composition, known compositions for forming insulating patterns can be used without particular limitation, but preferably contain at least one resin (hereinafter also referred to as "specific resin") selected from the group consisting of heterocyclic polymers and their precursors, more preferably containing polyimide or polyimide precursor.

[0517] The imidization rate of the above-mentioned polyimide precursor is preferably less than 50%.

[0518] The imidization rate of the above-mentioned polyimide is preferably 50% or higher.

[0519] Details regarding the imidization rate will be discussed later.

[0520] <Specific Resins>

[0521] The heterocyclic polymer is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

[0522] 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.

[0523] Examples of heterocyclic polymers include polyimide, polybenzoxazole, and polyamide-imide.

[0524] 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.

[0525] Examples of precursors for heterocyclic polymers include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

[0526] 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.

[0527] The composition preferably contains polyimide or a polyimide precursor as a specific resin.

[0528] The resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0529] 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.

[0530] Examples of polymerizable groups include groups with olefinic unsaturated bonds, epoxy groups, oxocyclic butyl groups, benzoxazolyl groups, etc., with groups having olefinic unsaturated bonds being preferred.

[0531] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0532] Among these, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, or maleimide are preferred, and (meth)acryloyl is more preferred from the viewpoint of reactivity. Furthermore, from the viewpoint of reducing dielectric loss tangent, vinylphenyl or maleimide is preferred.

[0533] Furthermore, certain resins may have polar conversion groups such as acid-decomposing groups.

[0534] 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.

[0535] 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 (4-1) and repeating units represented by formula (4-2).

[0536] [Chemical Formula 8]

[0537]

[0538] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each can be independently a hydrogen atom or a monovalent organic group.

[0539] [Chemical Formula 9]

[0540]

[0541] In equation (4-2), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of the two groups independently represents a structure containing polymeric groups, and n and m independently represent integers from 0 to 4.

[0542] -X 1 -

[0543] X 1 The carbon number is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0544] In equation (4-1), X 1 Preferably, it represents an organic group containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4).

[0545] Due to X 1 It contains an organic group that is formed by removing two or more hydrogen atoms from the structure represented by any one of formulas (V-1) to (V-4), thereby improving the chemical resistance and flatness of the cured product.

[0546] Furthermore, due to X 1 Organic groups containing structures formed by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4) can also achieve effects such as suppressing the generation of developing residues, reducing the dielectric constant of cured products, and reducing the coefficient of thermal expansion.

[0547] [Chemical Formula 10]

[0548]

[0549] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0550] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0551] In equation (V-2), R X1 Each of the components is preferably an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0552] In equation (V-3), R X2 and R X3 Hydrogen atoms are preferred individually.

[0553] When R X2 With R X3 When bonded to form a ring structure, R X2 With R X3 The structure formed by bonding is preferably a single bond, -O- or -C(R)2-, more preferably -O- or -C(R)2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, alkyl or aryl, and even more preferably a hydrogen atom.

[0554] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), 1 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (4-1). 1 In the bonding sites of the four carbonyl groups, n1 represents an integer from 0 to 5, and is preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0555] [Chemical Formula 11]

[0556]

[0557] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), 1Preferably, the group is represented by formula (V-2-1) or formula (V-2-2) below. From the viewpoint of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. In this specification, the bond that crosses the edge of the ring structure refers to the bond that replaces any one of the hydrogen atoms in the ring structure. In the following formula, L X1 The symbol represents a single bond or -O-, and * represents X in equation (4-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X1 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0558] [Chemical Formula 12]

[0559]

[0560] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), 1 Preferably, the group is represented by formula (V-3-1) or formula (V-3-2) below. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-2) is preferred. In the following formulas, * represents X in formula (4-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X2 and R X3 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0561] [Chemical Formula 13]

[0562]

[0563] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), 1 Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents X in formula (4-1). 1 The bonding sites of the four carbonyl groups are denoted by n1, which represents an integer from 0 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups. Preferably, in the structure represented by (V-4-1), none of the hydrogen atoms are substituted.

[0564] [Chemical Formula 14]

[0565]

[0566] In addition, X 1It can be the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride as described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0567] And, X 1 Preferably, the structure does not contain imide bonds.

[0568] And, X 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0569] In this invention, the carbamate bond refers to the bond formed by *-OC(=O)-NR. N -* indicates the key, R N Represents a hydrogen atom or a monovalent organic group, with * indicating the bonding site with a carbon atom. R N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.

[0570] 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 * indicates the bonding site with a carbon atom. R N The preferred method is as described above.

[0571] In addition, X 1 Preferably, the structure does not contain ester bonds.

[0572] In this invention, an ester bond refers to a bond represented by *-OC (=O)-*.

[0573] Among these, X 1 Preferably, it is free of imide bonds, carbamate bonds, urea bonds and amide bonds, and more preferably, it is free of imide bonds, carbamate bonds, urea bonds, amide bonds and ester bonds.

[0574] And, X 1 It can be a structure represented by the following equation (X-2), or a structure represented by (X-2) where X is a subset of X. 2 The hydrogen atom of the group represented by L 3 The hydrogen atoms of the group represented are represented by R in formula (4-1). 1 The structure is formed by the substitution of a group.

[0575] [Chemical Formula 15]

[0576]

[0577] In equation (X-2), X 2 Each independently represents a trivalent linker, L3 * indicates a divalent linker group, and * indicates a bonding site with other structures.

[0578] In equation (X-2), X 2 Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, these are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0579] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, haloalkylene, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, haloalkylene, arylene, or linking groups formed by bonding two or more of these.

[0580] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0581] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but it is preferred that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0582] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0583] And, X 2 Preferably, the compound is a tricarboxylic acid compound derived from at least one carboxyl group that can be halogenated. Chlorination is preferred as the halogenation method.

[0584] In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

[0585] Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-treated.

[0586] Examples of tricarboxylic acid compounds that can be halogenated include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

[0587] These tricarboxylic acid compounds can be used in one or more forms.

[0588] X 2 Preferably, the structure does not contain an imide structure.

[0589] And, X 2 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0590] In addition, X 2 Preferably, the structure does not contain ester bonds.

[0591] Among these, X 2 Preferably, it is free of imide structures, urethane bonds, urea bonds and amide bonds, and more preferably, it is free of imide structures, urethane bonds, urea bonds, amide bonds and ester bonds.

[0592] Specifically, the preferred tricarboxylic acid compound is a tricarboxylic acid compound containing a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a group formed by combining two or more of these groups through single bonds or linking groups. More preferably, it is a tricarboxylic acid compound containing an aromatic group with 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0593] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds formed by the linkage of phthalic acid (or phthalic anhydride) with benzoic acid through single bonds, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene oxide.

[0594] These compounds can be compounds formed by anhydride conversion of two carboxyl acids (e.g., trimellitic anhydride) or compounds formed by halogenation of at least one carboxyl group (e.g., trimellitic anhydride chloride).

[0595] In equation (X-2), L 3Examples include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, or groups formed by linking two or more of these groups through single bonds or linking groups. Preferably, these are straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more of these groups through single bonds or linking groups. More preferably, these are aromatic groups with 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups with 6 to 20 carbon atoms through single bonds or linking groups.

[0596] The preferred linking groups are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, haloalkylene, arylene, or linking groups formed by bonding two or more of these. More preferably, they are -O-, -S-, alkylene, haloalkylene, arylene, or linking groups formed by bonding two or more of these.

[0597] As the aforementioned alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred.

[0598] As the aforementioned alkyl halide, alkyl halide with 1 to 20 carbon atoms is preferred, alkyl halide with 1 to 10 carbon atoms is more preferred, and alkyl halide with 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned alkyl halide include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The aforementioned alkyl halide may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but it is preferred that all hydrogen atoms are replaced by halogen atoms. Examples of preferred alkyl halide include (ditrifluoromethyl)methylene, etc.

[0599] The aforementioned arylene group is preferably phenylene or naphthylene, more preferably phenylene, and even more preferably 1,3-phenylene or 1,4-phenylene.

[0600] And, X 1 It can be a structure represented by the following equation (X-3), or a structure represented by (X-3) where X is a subset of the structure. 2 The hydrogen atom of the group represented by L 3 The hydrogen atoms of the group represented are represented by R in formula (4-1). 1 The structure is formed by the substitution of a group.

[0601] [Chemical Formula 16]

[0602]

[0603] In equation (X-3), X 2Each independently represents a trivalent linker, L 3 * indicates a divalent linker group, and * indicates a bonding site with other structures.

[0604] In equation (X-3), X 2 and L 3 The preferred method is the same as X in equation (X-2). 2 and L 3 The preferred method is the same.

[0605] -Y 1 -

[0606] Y 1 The carbon number is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0607] In equation (4-1), Y 1 It can be a group containing a structure formed by removing two or more hydrogen atoms from the structure represented by any one of the above formulas (V-1) to (V-4).

[0608] Because of Y 1 It contains an organic group that is formed by removing two or more hydrogen atoms from the structure represented by any one of formulas (V-1) to (V-4), thereby improving the chemical resistance and flatness of the cured product.

[0609] When Y 1 When Y contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), 1 Preferably, it is a group represented by the following formula (V-1-2). In the following formula, * represents Y in formula (4-1). 1 The bonding sites of the two nitrogen atoms are denoted by n1, which is an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0610] [Chemical Formula 17]

[0611]

[0612] When Y 1 When Y contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), 1 Preferably, the group is represented by formula (V-2-3) or formula (V-2-4) below. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-2-4) is preferred. In the following formula, L X1 * indicates a single bond or -O-, and * indicates a Y in equation (4-1) 1 The bonding sites of the two nitrogen atoms. Furthermore, R X1The preferred configuration is as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0613] [Chemical Formula 18]

[0614]

[0615] When Y 1 When Y contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), 1 Preferably, the group is represented by formula (V-3-3) or formula (V-3-4). From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-3) is preferred. In the following formulas, * represents Y in formula (4-1). 1 The bonding sites of the two nitrogen atoms. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0616] [Chemical Formula 19]

[0617]

[0618] When Y 1 When Y contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), 1 Preferably, it is a group represented by the following formula (V-4-2) or formula (V-4-3). In the following formulas, * represents the group corresponding to Y in formula (4-1). 1 The bonding sites of the two nitrogen atoms are denoted by n1, which is an integer from 0 to 5. Furthermore, n1 being 0 is also one of the preferred embodiments of the present invention. Additionally, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0619] [Chemical Formula 20]

[0620]

[0621] In addition, Y 1 It can be the group described in paragraphs 0042 to 0053 of Japanese Patent Application Publication No. 2023-003421.

[0622] Furthermore, Y 1 Preferably, the structure does not contain imide bonds.

[0623] Furthermore, Y 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0624] In addition, Y 1 Preferably, the structure does not contain ester bonds.

[0625] Among these, Y 1 Preferably, it is free of imide bonds, carbamate bonds, urea bonds and amide bonds, and more preferably, it is free of imide bonds, carbamate bonds, urea bonds, amide bonds and ester bonds.

[0626] In these, X in equation (4-1) 1 and Y 1 Preferably, these organic groups contain organic groups that are structures formed by removing two or more hydrogen atoms from the structures represented by any one of the above formulas (V-1) to (V-4). The preferred embodiments of these groups are as described above.

[0627] R in equation (4-1) 1 and R 2 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. 1 and R 2 At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 1 and R 2 At 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.

[0628] 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.

[0629] [Chemical Formula 21]

[0630]

[0631] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0632] In equation (III), * indicates the bonding site with other structures.

[0633] In equation (III), R 201It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0634] 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.

[0635] 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.

[0636] When polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0637] 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.

[0638] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0639] 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.

[0640] 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.

[0641] In equation (4-1), when R 1 When it is a hydrogen atom or R 2When the hydrogen atom is present, the polyimide precursor can form a salt pair with a tertiary amine compound having an olefinically unsaturated bond. An example of such a tertiary amine compound with an olefinically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0642] In equation (4-1), R 1 and R 2 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.

[0643] 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.

[0644] 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.

[0645] 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.

[0646] In equation (4-2), X 1 and Y 1 The preferred method is the same as X in equation (4-1) 1 and Y 1 The preferred method is the same.

[0647] In equation (4-2), R 1 The preferred manner of the polymeric groups in the resin is as described above.

[0648] In equation (4-2), R 1 Preferably, it is a group represented by formula (R-1).

[0649] [Chemical Formula 22]

[0650]

[0651] In equation (R-1), L 1 A represents an a1+1 valence linker group.1 The group represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents the group with respect to X in equation (1-1). 1 Or Y 1 The bonding sites.

[0652] In equation (R-1), L 1 Preferably, it is a group represented by the following formula (L-2).

[0653] [Chemical Formula 23]

[0654]

[0655] In equation (L-2), Z 2 Indicates -O-, -NR N -, -C(=O)O-or-C(=O)NR N -, R N L represents a hydrogen atom or a monovalent organic group. When a1 is 1, L x Indicates a single bond or a divalent linker; when a1 is 2 or more, L x This represents a1+1 valence linker, where a1 represents an integer greater than or equal to 1, and * represents the linkage with X in equation (1-1). 1 Or Y 1 Other bonding sites in the structure, # indicates the bonding with A in equation (R-1) 1 The bonding sites.

[0656] In equation (L-2), Z 2 Preferably -O- or -C(=O)O-. And, when Z 2 For -NR N - At that time, R N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and even more preferably a hydrogen atom.

[0657] In equation (L-2), when a1 is 1, L x Preferably, it is an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.

[0658] In equation (L-2), when a1 is 2 or more, L x Preferably, it is a hydrocarbon group, a heterocyclic group, or a combination thereof, more preferably a saturated aliphatic hydrocarbon group with 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group with 3 to 15 carbon atoms.

[0659] In equation (L-2), the meaning of a1 is the same as that of a1 in equation (R-1).

[0660] In equation (R-1), A 1This indicates a polymerizable group. The preferred manner in which the polymerizable group is present is as described above for the polymerizable group found in the resin.

[0661] Here, A 1 Preferably, it is (meth)acryloyloxy, maleimide, or vinylphenyl. From the viewpoint of reducing the dielectric loss tangent of the cured product, maleimide or vinylphenyl is more preferred. Furthermore, from the viewpoint of reactivity, (meth)acryloyloxy is more preferred.

[0662] Among these, A in formula (R-1) is preferred. 1 It is vinylphenyl and L 1 The group is represented by formula (L-2-1).

[0663] [Chemical Formula 24]

[0664]

[0665] In equation (L-2-1), L X2 'a1' represents a hydrocarbon group, and 'a1' represents an integer greater than or equal to 1.

[0666] In equation (L-2-1), L X2 Preferably, it contains aliphatic saturated hydrocarbon groups.

[0667] When a1 is 1, L X2 Preferably, it is an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.

[0668] In equation (L-2-1), the meaning of a1 is the same as that of a1 in equation (R-1).

[0669] Furthermore, preferably, A in formula (R-1) 1 Maleimide group, L 1 For the group represented by formula (L-2), L X It is an aromatic group or an aliphatic saturated hydrocarbon group with 4 or more carbon atoms.

[0670] The aromatic group can be any of the aromatic hydrocarbon group or the aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group.

[0671] As an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group with 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group with 6 carbon atoms.

[0672] Examples of heteroatoms in aromatic heterocyclic groups include oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the aromatic heterocyclic group is preferably one or two. Furthermore, the aromatic heterocyclic group is preferably a five-membered or six-membered ring containing the aforementioned heteroatoms. In addition, the aromatic heterocyclic group can be fused with other aromatic heterocyclic groups or other aromatic hydrocarbon cyclic groups.

[0673] As an aliphatic saturated hydrocarbon group with 4 or more carbon atoms, it can be any of the following structures: straight-chain, branched-chain, cyclic, or a combination thereof.

[0674] The aliphatic saturated hydrocarbon group with 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms.

[0675] In formula (R-1), a1 is preferably an integer from 1 to 4, and more preferably an integer from 1 to 2. Furthermore, a1 being 1 is also one of the preferred embodiments of the present invention.

[0676] Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0677] -n and m-

[0678] In equation (4-2), m is preferably an integer from 0 to 2, more preferably 0 or 1. Furthermore, m being 0 is also one of the preferred embodiments of the present invention.

[0679] In equation (4-2), n is preferably 1 or 2, and more preferably 2.

[0680] [Polyimide precursor]

[0681] The type of polyimide precursor used in this invention is not particularly limited, but it is preferred to contain repeating units represented by the above formula (4-1).

[0682] The polyimide precursor may contain one repeating unit represented by formula (4-1), or two or more repeating units represented by formula (4-1). Furthermore, it may contain structural isomers of the repeating unit represented by formula (4-1). In addition to the repeating unit represented by formula (4-1), the polyimide precursor may also contain other types of repeating units.

[0683] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (4-1) 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 precursor except for the terminal units can be repeating units represented by formula (4-1).

[0684] - Cyclization rate (imideization rate) -

[0685] 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%.

[0686] The lower limit of the cyclization rate mentioned above is not specifically limited and can be 0%.

[0687] The cyclization rate described above can be determined, for example, by the following method.

[0688] 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.

[0689] Cycloning rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0690] 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.

[0691] 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.

[0692] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0693] 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.

[0694] [Polyimide]

[0695] 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.

[0696] 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.

[0697] 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.

[0698] -Fluorine atom-

[0699] From the viewpoint of the membrane strength of the obtained organic membrane, polyimide is also preferably provided with fluorine atoms.

[0700] Fluorine atoms are preferably included, for example, in the repeating unit represented by formula (4-2) as R. 132 Or R in the repeating unit represented by equation (4-2) 131 More preferably, R is included in the repeating unit represented by equation (4). 132 Or R in the repeating unit represented by equation (4-2) 131 It is used as a fluorinated alkyl group.

[0701] 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.

[0702] -Silicon atom-

[0703] From the viewpoint of the strength of the obtained organic membrane, polyimide is also preferably composed of silicon atoms.

[0704] Silicon atoms are preferably contained, for example, in the repeating unit represented by equation (4-2) described later. 1 More preferably, Y is included in the repeating unit represented by equation (4-1) described later. 1 The structure is referred to later as an organically modified (poly)siloxane.

[0705] 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.

[0706] 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.

[0707] -ene unsaturated bond-

[0708] From the viewpoint of the strength of the obtained organic membrane, polyimide preferably has olefinic unsaturated bonds.

[0709] 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.

[0710] The aforementioned olefinic unsaturated bonds preferably possess free radical polymerization properties.

[0711] The olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4-2) with X. 1 Or Y 1 More preferably, it is included in X. 1 or RY 1 It is a group with an olefinic unsaturated bond.

[0712] 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.

[0713] - Polymerizable groups other than those with olefinic unsaturated bonds-

[0714] Polyimides can have polymerizable groups other than those with olefinic unsaturated bonds.

[0715] 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.

[0716] Polymerizable groups other than those with olefinic unsaturated bonds, preferably R in the repeating unit represented by formula (4) described later. 131 middle.

[0717] 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.

[0718] -Polar switching group-

[0719] 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 (4-1) above. 1 and R 2 The acid-decomposing groups described herein are the same, and the preferred methods are also the same.

[0720] Polar conversion groups, for example, are contained in the repeating unit represented by formula (4-2) described later.1 R 2 In the end of polyimide, etc.

[0721] -Acid Value-

[0722] 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.

[0723] 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.

[0724] 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.

[0725] The acid value is determined by a known method, for example by the method described in JIS K 0070:1992.

[0726] 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.

[0727] 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.

[0728] When the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0729] 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.

[0730] -Phenolic hydroxyl-

[0731] From the viewpoint of achieving an appropriate development speed using alkaline developing solution, polyimide preferably has phenolic hydroxyl groups.

[0732] Polyimide can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0733] Phenolic hydroxyl groups are preferably included, for example, in the repeating unit represented by formula (4-2) as R. 132 or R 131 middle.

[0734] 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.

[0735] 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 above formula (4-2).

[0736] 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.

[0737] 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.

[0738] 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.

[0739] -Imidization rate (ring-closure rate)-

[0740] 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.

[0741] The upper limit of the imidization rate is not particularly limited; it can be below 100%.

[0742] The imidization rate described above was determined using the method described above.

[0743] Polyimide can contain R consisting of all repeating units 1 and R 2 The repeating units represented by the above equation (4-2) with the same combination can also contain R consisting of two or more types. 1 and R 2 The repeating units represented by the above formula (4-2) can be different combinations. In addition to the repeating units represented by the above formula (4-2), polyimide may also contain other types of repeating units. For example, the repeating units represented by the above formula (4-1) can be cited as other types of repeating units.

[0744] 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.

[0745] 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.

[0746] 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.

[0747] 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.

[0748] 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.

[0749] [Polybenzoxazole precursor]

[0750] 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.

[0751] [Polybenzoxazole]

[0752] As polybenzoxazoles, examples include compounds described in paragraphs 0101 to 0108 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0753] [Polyamide-imide precursor]

[0754] 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.

[0755] [Polyamide-imide]

[0756] 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.

[0757] [Methods for manufacturing polyimide precursors, etc.]

[0758] 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.

[0759] 〔content〕

[0760] 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.

[0761] 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.

[0762] The composition preferably contains at least two resins.

[0763] 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.

[0764] 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 (X in the above formula (24-1)). 1 Two or more different polyimide precursors.

[0765] <Other Resins>

[0766] 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").

[0767] 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.

[0768] 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.

[0769] 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).

[0770] 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.

[0771] When the composition contains other resins, the content of the 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.

[0772] 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.

[0773] 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.

[0774] <Polymerizing compounds>

[0775] The composition preferably contains a polymerizable compound.

[0776] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0777] [Free radical crosslinking agent]

[0778] The composition preferably contains a free radical crosslinking agent.

[0779] 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.

[0780] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from a reactivity point of view.

[0781] 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.

[0782] 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.

[0783] 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.

[0784] 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.

[0785] 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.

[0786] 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.

[0787] 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.

[0788] 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.

[0789] 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.

[0790] 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.

[0791] 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.

[0792] 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.

[0793] 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").

[0794] 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.

[0795] In this invention, the carbamate bond refers to the bond formed by *-OC(=O)-NR. N-* indicates the key, R N The symbol represents a hydrogen atom or a monovalent organic group, and * indicates the bonding site with a carbon atom, respectively.

[0796] Compositions containing crosslinking agent U can sometimes improve chemical resistance, resolution, etc.

[0797] 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.

[0798] 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.

[0799] 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.

[0800] 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.

[0801] 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.

[0802] 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.

[0803] 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.

[0804] 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.

[0805] 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.

[0806] 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.

[0807] The polymerizability of the crosslinking agent U is preferably 210–400 g / mol, more preferably 220–400 g / mol.

[0808] The crosslinking agent U is preferably a structure represented by, for example, the following formula (U-1).

[0809] [Chemical Formula 25]

[0810]

[0811] 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.

[0812] R U1 Hydrogen atoms, alkyl or aromatic hydrocarbon groups are preferred, and hydrogen atoms are more preferred.

[0813] R N Hydrogen atoms, alkyl or aromatic hydrocarbon groups are preferred, and hydrogen atoms are more preferred.

[0814] 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.

[0815] 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.

[0816] Z U2 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.

[0817] 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.

[0818] 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.

[0819] 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.

[0820] m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0821] The crosslinking agent U is preferably composed of at least one of hydroxyl, alkeneoxy, amide and cyano groups.

[0822] 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.

[0823] 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.

[0824] 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.

[0825] 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.

[0826] 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.

[0827] 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").

[0828] 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").

[0829] 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.

[0830] 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.

[0831] 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.

[0832] From the viewpoint of compatibility with heterocyclic polymers, the crosslinking agent U preferably contains aromatic groups.

[0833] 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.

[0834] 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.

[0835] 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.

[0836] 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.

[0837] Nitrogen, oxygen, or sulfur atoms are preferred as heteroatoms contained in the aforementioned aromatic heterocyclic groups.

[0838] 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.

[0839] 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.

[0840] 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.

[0841] 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.

[0842] [Chemical Formula 26]

[0843]

[0844] [Axis of symmetry]

[0845] The crosslinking agent U is preferably a compound without a symmetry axis.

[0846] 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.

[0847] 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.

[0848] [Molecular weight]

[0849] 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.

[0850] 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.

[0851] The following are specific examples of crosslinking agent U, but crosslinking agent U is not limited to these.

[0852] [Chemical Formula 27]

[0853]

[0854] [Chemical Formula 28]

[0855]

[0856] [Chemical Formula 29]

[0857]

[0858] From the viewpoint of pattern resolution and film stretchability, the composition preferably uses difunctional methacrylates or acrylates.

[0859] 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 EO-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0860] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0861] 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.

[0862] 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.

[0863] 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.

[0864] 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.

[0865] [Other crosslinking agents]

[0866] The composition also preferably contains other crosslinking agents that are different from the free radical crosslinking agents described above.

[0867] 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.

[0868] 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.

[0869] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0870] [Polymerization initiator]

[0871] The composition preferably contains a polymerization initiator.

[0872] The polymerization initiator can be either a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferred to contain a photopolymerization initiator.

[0873] 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.

[0874] 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.

[0875] 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.

[0876] 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.

[0877] 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.

[0878] 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.

[0879] 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.

[0880] 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.

[0881] 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.

[0882] 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.

[0883] 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)-.

[0884] [Chemical Formula 30]

[0885]

[0886] 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.

[0887] [Chemical Formula 31]

[0888]

[0889] [Chemical Formula 32]

[0890]

[0891] 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.

[0892] 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.

[0893] 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.

[0894] 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.

[0895] 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.

[0896] [Sensitizer]

[0897] 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.

[0898] 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.

[0899] 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.

[0900] In addition, other sensitizing pigments can also be used.

[0901] 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.

[0902] 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.

[0903] [Chain transfer agent]

[0904] 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.

[0905] 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.

[0906] 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. There may be only one type of chain transfer agent, or there may be two or more types. When there are two or more types of chain transfer agents, it is preferable that their total content falls within the above-mentioned range.

[0907] Furthermore, having two or more polymerization initiators in the composition is also one of the preferred embodiments of the present invention.

[0908] 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.

[0909] 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.

[0910] 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.

[0911] By incorporating photoradical polymerization initiators and photoacid-producing agents, properties such as resolution can sometimes be improved.

[0912] 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.

[0913] [Thermal polymerization initiator]

[0914] 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.

[0915] 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.

[0916] 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.

[0917] <Alkali-producing agent>

[0918] 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.

[0919] 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.

[0920] 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.

[0921] 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.

[0922] 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.

[0923] The following compounds can be cited as alkali-producing agents, but are not limited to these.

[0924] [Chemical Formula 33]

[0925]

[0926] 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.

[0927] 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.

[0928] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[0929] [Chemical Formula 34]

[0930]

[0931] The following compounds can be cited as specific examples of imine salts, but are not limited to these.

[0932] [Chemical Formula 35]

[0933]

[0934] 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.

[0935] 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.

[0936] 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.

[0937] One or more alkali-producing agents can be used. When two or more are used, the total amount is preferably within the above range.

[0938] <Solvent>

[0939] The composition preferably contains a solvent.

[0940] 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.

[0941] 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.

[0942] 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.

[0943] Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0944] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred cyclic hydrocarbons.

[0945] As a sulfoxide, dimethyl sulfoxide can be cited as a preferred sulfoxide.

[0946] 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.

[0947] Examples of preferred urea compounds include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0948] 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.

[0949] From the perspective of improving the properties of the coating surface, it is also preferable to use a mixture of two or more solvents.

[0950] In this invention, the solvent is preferably selected from one of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucosidone, and dihydro-L-glucosidone, or a mixed solvent consisting of two or more of these 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.

[0951] 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.

[0952] 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.

[0953] 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.

[0954] <Metal Adhesion Modifier>

[0955] 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.

[0956] [Silane coupling agent]

[0957] 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.).

[0958] [Chemical Formula 36]

[0959]

[0960] 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.

[0961] Furthermore, as a silane coupling agent, compounds of oligomer type having multiple alkoxysilyl groups can also be used.

[0962] Examples of this type of oligomer include compounds containing repeating units represented by the following formula (S-1).

[0963] [Chemical Formula 37]

[0964]

[0965] 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.

[0966] 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.

[0967] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[0968] n represents an integer from 0 to 2, preferably 1.

[0969] Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer type compound can be the same.

[0970] 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.

[0971] As for this type of oligomer compound, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0972] [Aluminum-based adhesive additives]

[0973] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate diisopropoxide aluminum.

[0974] 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.

[0975] 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.

[0976] <Migration Inhibitor>

[0977] 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.

[0978] 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.

[0979] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0980] Other migration inhibitors include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are incorporated herein by reference.

[0981] The following compounds can be cited as specific examples of migration inhibitors.

[0982] [Chemical Formula 38]

[0983]

[0984] [Chemical Formula 39]

[0985]

[0986] 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.

[0987] 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.

[0988] <Polymerization Inhibitor>

[0989] 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.

[0990] 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.

[0991] 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.

[0992] 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.

[0993] [Urea compounds, carbodiimide compounds, isourea compounds]

[0994] 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.").

[0995] In these compositions, the composition preferably also contains a compound having a urea bond.

[0996] The urea compounds mentioned here do not include the polymerizable compounds mentioned above, or compounds corresponding to silane coupling agents.

[0997] Examples of urea compounds include those described in paragraphs 0334 to 0339 of International Publication No. 2022 / 070730.

[0998] Specific examples of urea compounds include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, etc., but are not limited to these.

[0999] 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.

[1000] 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.

[1001] <Light Absorber>

[1002] The composition also preferably contains a compound (light absorber) that reduces the absorbance of its exposure wavelength due to exposure.

[1003] Examples of light absorbers include compounds described in paragraphs 0159 to 0183 of International Patent Publication No. 2022 / 202647 and compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are included in this specification.

[1004] 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.

[1005] The following are specific examples of photochromic compounds, but the present invention is not limited thereto.

[1006] [Chemical Formula 40]

[1007]

[1008] 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.

[1009] <Other Additives>

[1010] 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.

[1011] <Characteristics of the Composition>

[1012] 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... 2If 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.

[1013] <Limitations Regarding Substances Contained in the Composition>

[1014] 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.

[1015] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[1016] 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.

[1017] 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.

[1018] 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.

[1019] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[1020] 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 layers of six different resins, or bottles with a seven-layer structure formed by six different resins, are also preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[1021] <Preparation of the Composition>

[1022] 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.

[1023] Examples of mixing methods include mixing using stirring blades, mixing using a ball mill, and mixing by rotating a tank.

[1024] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[1025] 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.

[1026] 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. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[1027] After filtration, the composition filled in the bottle can be degassed under reduced pressure.

[1028] Example

[1029] 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.

[1030] <Resin Synthesis>

[1031] [Synthesis Example: Synthesis of Polymer 1]

[1032] 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. 1H-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%.

[1033] [Chemical Formula 41]

[1034]

[1035] [Synthesis Example: Synthesis of Polymer 2]

[1036] -Synthesis of diamine 2a for polymer 2 synthesis-

[1037] 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.

[1038] The structure of 2b is shown below. (From...) 1 H-NMR spectroscopy confirmed the following structure.

[1039] 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)

[1040] [Chemical Formula 42]

[1041]

[1042] 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.

[1043] 1 H-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)

[1044] [Chemical Formula 43]

[1045]

[1046] -Synthesis of Polymer 2-

[1047] 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.

[1048] [Chemical Formula 44]

[1049]

[1050] [Synthetic Examples: Synthesis of Polymers 5 to 7]

[1051] Polymers 5 through 7 were synthesized using the same method as polymer 2, except that the raw materials used were appropriately modified.

[1052] Polymers 5 through 7 are resins 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. The weight-average molecular weight, number-average molecular weight, and imidization rate of these resins are listed in the table below.

[1053] [Chemical Formula 45]

[1054]

[1055] [Table 1]

[1056]

[1057] [Synthetic Example: Synthesis of Polymer 3]

[1058] 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.

[1059] 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%.

[1060] [Chemical Formula 46]

[1061]

[1062] [Synthetic Example: Synthesis of Polymer 4]

[1063] 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.

[1064] 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%.

[1065] [Chemical Formula 47]

[1066]

[1067] [Synthetic Example: Synthesis of Polymer 8]

[1068] 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.

[1069] 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.

[1070] 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%.

[1071] [Chemical Formula 48]

[1072]

[1073] [Synthetic Examples: Synthesis of Polymers 9 to 16]

[1074] With appropriate changes to the raw materials used, polymers 9 through 15 were synthesized using the same method as polymer 3.

[1075] Polymers 9 through 15 are resins 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. The weight-average molecular weight, number-average molecular weight, and imidization rate of these resins are listed in the table below.

[1076] [Chemical Formula 49]

[1077]

[1078] [Chemical Formula 50]

[1079]

[1080] [Chemical Formula 51]

[1081]

[1082] [Chemical Formula 52]

[1083]

[1084] [Table 2]

[1085]

[1086] <Examples and Comparative Examples>

[1087] In each embodiment, the components listed in the table below were mixed to obtain each negative photosensitive resin composition.

[1088] 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.

[1089] The obtained negative photosensitive resin composition was pressure filtered using a polypropylene filter with a pore width of 0.45 μm.

[1090] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[1091] [Table 3]

[1092]

[1093] [Table 4]

[1094]

[1095] [Table 5]

[1096]

[1097] [Table 6]

[1098]

[1099] The detailed information of each component recorded in the table is as follows.

[1100] [Polymer (Resin)]

[1101] • Polymers 1 to 16: Polymers 1 to 16 synthesized in the above manner

[1102] [Polymerizing compounds]

[1103] • Polymerizable compound 1: A compound with the following structure

[1104] • Polymerizable compound 2: Compounds with the following structures (in the following structures, the numbers indicate the molar ratio of each structure).

[1105] • Polymerizable compounds 3–8: Compounds with the following structures

[1106] [Chemical Formula 53]

[1107]

[1108] [Chemical Formula 54]

[1109]

[1110] [Polymerization initiator]

[1111] • Polymerization initiators 1-4: Compounds with the following structures

[1112] • Polymerization initiator 5: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1113] [Chemical Formula 55]

[1114]

[1115] [Migration Inhibitor]

[1116] • Migration inhibitors 1-6: Compounds with the following structures

[1117] [Chemical Formula 56]

[1118]

[1119] [Metal Adhesion Modifier]

[1120] • Metal adhesion modifiers 1-3: Compounds with the following structures

[1121] [Chemical Formula 57]

[1122]

[1123] [Light absorber]

[1124] • Light absorber 1: A compound with the following structure

[1125] • Light absorber 2:1~2: 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'-hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid ester (NQD (naphthoquinone diazide))

[1126] [Chemical Formula 58]

[1127]

[1128] [Organotitanium compounds]

[1129] Organotitanium compound 1: Compounds with the following structure

[1130] Organotitanium compound 2: TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[1131] [Chemical Formula 59]

[1132]

[1133] [Polymerization inhibitor]

[1134] • Inhibitors 1-4: Compounds with the following structures

[1135] [Chemical Formula 60]

[1136]

[1137] [Alkali-producing agent]

[1138] Alkali-producing agents 1-3: Compounds with the following structures

[1139] [Chemical Formula 61]

[1140]

[1141] [Solvent]

[1142] Solvent 1: GBL (γ-butyrolactone)

[1143] Solvent 2: NMP (N-methyl-2-pyrrolidone)

[1144] Solvent 3: DMSO (dimethyl sulfoxide)

[1145] Solvent 4: EL (ethyl lactate)

[1146] Solvent 5: γ-valerol

[1147] Solvent 6: 3-Methoxy-N,N-Dimethylpropionamide

[1148] Solvent 7: Anisole

[1149] [surfactants]

[1150] Surfactant 1: BYK-333 (manufactured by BYK Corporation)

[1151] <Evaluation>

[1152] [Determination of cone angle]

[1153] In each embodiment, the composition was applied by spin coating and dried at 100°C for 5 minutes, thereby forming a uniform resin composition layer with a thickness of 5 μm on a silicon wafer.

[1154] In each comparative example, a uniform resin composition layer was formed in the same manner as in Example 14, except that the same composition was used.

[1155] Using an i-ray stepper (manufactured by Canon Inc.: FPR-3000i5), the resin composition layer on the silicon wafer was exposed through a mask with a circular mask portion having a diameter of 5 μm, using the numerical aperture (Na) recorded in the "Exposure Na" column of the table below, the exposure illuminance recorded in the "Exposure Illuminance" column of the table, and the exposure amount recorded in the "Exposure Amount" column of the table.

[1156] Subsequently, cyclopentanone was used as the developer for 15 seconds, and PGMEA was used as the rinse solution for 30 seconds to obtain the precursor pattern of the insulating pattern.

[1157] Furthermore, an insulating pattern was obtained by heating at 230°C for 3 hours in a nitrogen environment.

[1158] A 50 nm thick Ti layer is formed as a conductive layer by sputtering in the area between and on the insulating patterns formed above, and a 200 nm thick Cu layer is formed on it by plating. Then, a Cu layer (conductive layer) with a thickness of 2500 nm is formed by plating on the Cu layer.

[1159] Using CMP (Chemical Mechanical Polishing) manufactured by Fujikoshi Machinery Corp., silica was used as the slurry and the above conductive layer was polished for 2.5 minutes at a polishing pressure of 3 psi, thereby exposing the insulating pattern, the Ti layer formed as a seed layer, and the conductive pattern (through-hole pattern) formed in the area between the insulating patterns to the surface.

[1160] In this specification, 1 psi is 6.895 kPa.

[1161] In each embodiment and comparative example, the insulating pattern and the conductive pattern were cut on a face including the center of the conductive pattern. After the cross-section was ground using an ArBlade5000 milling machine (manufactured by Hitachi, Ltd.), SEM images were acquired using a FE-SEM SU-4800 (manufactured by Hitachi, Ltd.), and the angle (cone angle) between the bottom surface of the insulating pattern and the side surface of the insulating pattern was measured. The measurement results are recorded in the "Through Hole Cone Angle (degrees)" column.

[1162] [uHAST test (unsaturated vapor pressure test)]

[1163] The compositions prepared in each embodiment were applied by spin coating to the exposed surface of a substrate comprising a semiconductor die and a sealing material, and dried at 100°C for 5 minutes to form a uniform resin composition layer with a thickness of 5 μm.

[1164] In each comparative example, a uniform resin composition layer was formed in the same manner as in Example 14, except that the same composition was used. Then, an i-ray stepper (manufactured by Canon Inc.: FPR-3000i5) was used to expose the resin composition at NA 0.16 and an exposure illuminance of 10000 W / m². 2 Exposure 400mJ / cm 2 The entire surface is exposed, and in addition to the exposure of the entire surface, development, washing and heating are performed using the same method as in the measurement of the cone angle described above, thereby forming a flat insulating film on the silicon wafer.

[1165] On this insulating film, insulating and conductive patterns are then formed using the same method as in the measurement of the cone angle described above.

[1166] Subsequently, the composition was coated again, and the entire surface was exposed, developed, rinsed, and heat-treated to produce a laminate for reliability testing.

[1167] A schematic cross-sectional view of the resulting laminate is shown below. Figure 8.

[1168] exist Figure 8 In this process, a first insulating film 202 is formed on the surface of the substrate 200, which includes semiconductor chips and sealing material, where the semiconductor chips are exposed. An insulating layer 208, which includes wiring with insulating patterns 204 and conductive patterns 206, is formed on the side of the substrate 200, which includes semiconductor chips and sealing material, opposite to the surface where the semiconductor chips are exposed. Furthermore, a second insulating layer 210 is formed on the side of the insulating layer 208, which includes wiring, opposite to the first insulating layer 202.

[1169] After 198 hours, 396 hours, and 594 hours at 130℃ and 85% relative humidity, the cross-section of the wiring section of the obtained laminate was observed by SEM (scanning electron microscope) to confirm the presence of any abnormalities such as cracks, peeling, and voids.

[1170] The evaluation should be conducted according to the following evaluation criteria, and the evaluation results should be recorded in the "uHAST test" column of the table.

[1171] -Evaluation Criteria-

[1172] A: After 594 hours, the cross-section of the wiring was observed by SEM, and no abnormalities such as cracks, peeling, or voids were found.

[1173] B: After 594 hours, the cross-sectional SEM results of the wiring revealed abnormalities such as cracks, peeling, and voids. However, after 396 hours, the cross-sectional SEM of the wiring did not reveal any abnormalities such as cracks, peeling, or voids.

[1174] C: After 396 hours, the cross-sectional SEM results of the wiring revealed abnormalities such as cracks, peeling, and voids. However, after 198 hours, the cross-sectional SEM of the wiring did not reveal any abnormalities such as cracks, peeling, or voids.

[1175] [HTS test (high temperature storage test)]

[1176] After 500 hours, 1000 hours, and 1500 hours at 150°C, the cross-section of the wiring section of the same laminate used in the uHAST test was observed by SEM (scanning electron microscope) to confirm the presence of any abnormalities such as cracks, peeling, or voids.

[1177] The evaluation should be conducted according to the following evaluation criteria, and the evaluation results should be recorded in the "HTS Test" column of the table.

[1178] -Evaluation Criteria-

[1179] A: After 1500 hours, the cross-section of the wiring was observed using SEM, and no abnormalities such as cracks, peeling, or voids were found.

[1180] B: After 1500 hours, the cross-sectional SEM results of the wiring revealed abnormalities such as cracks, peeling, and voids. However, after 1000 hours, the cross-sectional SEM of the wiring did not reveal any abnormalities such as cracks, peeling, or voids.

[1181] C: After 1000 hours, the cross-sectional SEM results of the wiring revealed abnormalities such as cracks, peeling, and voids. However, after 500 hours, the cross-sectional SEM of the wiring did not reveal any abnormalities such as cracks, peeling, or voids.

[1182] [Thermal Cycling Test]

[1183] A temperature cycling test of -40°C to 125°C was conducted on the same laminate used in the uHAST test described above, using a thermal shock testing apparatus (COSMOPIA S) (manufactured by Hitachi Global Life Solutions, Inc.).

[1184] At the 750, 1500, and 2250 cycle points, the cross-section of the wiring section was observed using SEM (scanning electron microscope) to confirm the presence of any abnormalities such as cracks, peeling, or voids.

[1185] The evaluation shall be conducted according to the following evaluation criteria, and the evaluation results shall be recorded in the "Thermal Cycling Test" column of the table.

[1186] -Evaluation Criteria-

[1187] A: After 2250 cycles, the cross-section of the wiring was observed by SEM, and no abnormalities such as cracks, peeling, or voids were found.

[1188] B: After 2250 cycles, the cross-sectional SEM results of the wiring revealed abnormalities such as cracks, peeling, and voids. However, after 1500 cycles, the cross-sectional SEM of the wiring did not reveal any abnormalities such as cracks, peeling, or voids.

[1189] C: After 1500 cycles, the cross-sectional SEM results of the wiring revealed abnormalities such as cracks, peeling, and voids. However, after 750 cycles, the cross-sectional SEM of the wiring did not reveal any abnormalities such as cracks, peeling, or voids.

[1190] [Table 7]

[1191]

[1192] [Table 8]

[1193]

[1194] (Example 101)

[1195] The number of semiconductor chips in the semiconductor package of Example 1 was changed from one to two, but the semiconductor package was fabricated under the same conditions as in Example 1. The evaluation results were the same as in Example 1.

[1196] The results above show that the semiconductor package of the present invention exhibits good results in uHAST test, HTS test and thermal cycling test.

[1197] In Comparative Example 1, the cone angle is less than 70°. It can be seen that, according to this method, the results in HTS and thermal cycling tests are poor.

[1198] In Comparative Example 2, the cone angle exceeds 110°. It is evident that, according to this method, the results in the uHAST and HTS tests are poor.

[1199] Symbol Explanation

[1200] 10-Rewiring layer A, 12-Insulating pattern A, 14-Conductive pattern A, 16-Conductive pad, 18-Exposed portion, 20-Semiconductor package, 22-Sealing layer, 24-Conductive connection, 26-Substrate, 28-Semiconductor die, 30-Sealing material, 32-Electrode, 34-Other conductive connection, 36-Conductive through-hole, 38-Other semiconductor die, 40-Other conductive pad, 42-Other conductive connection, 44-Insulating layer, 46-Composed of curable resin composition The formed layers are: 62-carrier wafer, 64-second carrier wafer, 102-conductive connection, 104-conductive pad, 106-insulating pattern A in the outermost layer of redistribution layer A, 108-conductive pattern A in the outermost layer of redistribution layer A, 110-solder component, 112-pillar, 200-substrate including semiconductor die and sealing material, 202-first insulating film, 204-insulating pattern, 206-conductive pattern, 208-insulating layer including wiring, and 210-second insulating layer.

Claims

1. A semiconductor package having: A sealing layer comprising at least one semiconductor die and a sealing material; A rewiring layer A is provided, which is in contact with at least one of the semiconductor chips and is connected to the circuit of the semiconductor chip. A conductive connection portion, which is connected to the redistribution layer A; and A substrate, which is connected to the conductive connection portion. The rewiring layer A is formed by stacking layers comprising an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A. The insulating pattern A has a through-hole structure, and the angle between the side surface of the through-hole structure and the bottom surface of the insulating pattern A is 70° to 110°.

2. The semiconductor package according to claim 1, wherein, The sealing layer comprises two or more semiconductor chips and a sealing material, and the circuits of two or more of the two or more semiconductor chips are connected to the redistribution layer A.

3. The semiconductor package according to claim 1, further comprising one or more semiconductor grains connected to the redistribution layer A, the semiconductor grains being located outside the sealing layer.

4. The semiconductor package according to claim 1, wherein, The rewiring layer A comprises a stacked structure of four or more layers.

5. The semiconductor package according to any one of claims 1 to 3, wherein, The wiring in the rewiring layer A includes a line pattern, the minimum line width of which is 0.1 μm to 10 μm.

6. The semiconductor package according to any one of claims 1 to 3, wherein, The insulating pattern A comprises a resin having repeating units represented by the following formula (1-1), [Chemical Formula 1] In formula (1-1), X 1 represents an organic group having 4 or more carbon atoms, Y 1 represents an organic group having 4 or more carbon atoms.

7. The semiconductor package according to claim 6, wherein, X in formula (1-1) 1 and Y 1 each independently is an organic group containing a structure obtained by removing 2 or more hydrogen atoms from any one of the structures represented by formulae (V-1) to (V-4) below, [Chemical Formula 2] In formula (V-2), R X1 each independently is a hydrogen atom, an alkyl group or a haloalkyl group, In formula (V-3), R X2 and R X3 each independently represent a hydrogen atom or a substituent, R X2 and R X3 may be bonded to form a ring structure.

8. A method for manufacturing a semiconductor package, comprising: In the sealing layer formation process, a semiconductor die is embedded in a sealing material to form a sealing layer in which a circuit with the semiconductor die exposed on one side and a circuit with the semiconductor die not exposed on the other side. In the process of forming redistribution layer A, a layer comprising an insulating pattern A and a conductive pattern A existing between the patterns of the insulating pattern A is stacked on the exposed surface of the sealing layer to form redistribution layer A. In the connection forming process, a conductive connection is formed on the surface of the redistribution layer A that is different from the surface that contacts the sealing layer; and The process of connecting the connecting part to the substrate. The process of forming the rewiring layer A includes a process of forming a through-hole structure using the insulating pattern A, wherein the angle between the side surface of the through-hole structure and the bottom surface of the insulating pattern A is 70° to 110°.

9. The method for manufacturing a semiconductor package according to claim 8, wherein, The insulating pattern A is formed using a negative photosensitive resin composition.

10. The method for manufacturing a semiconductor package according to claim 9, wherein, The negative photosensitive resin composition contains a resin having at least one repeating unit selected from repeating units represented by formula (4-1) and repeating units represented by formula (4-2). [Chemical Formula 3] In equation (4-1), X 1 Y is a tetravalent organic group. 1 R is a divalent organic group. 1 and R 2 Each can be independently a hydrogen atom or a monovalent organic group. [Chemical Formula 4] In equation (4-2), X 1 Y represents an organic group with 4 or more carbon atoms. 1 R represents an organic group with 4 or more carbon atoms. 1 Each of the two groups independently represents a structure containing polymeric groups, and n and m independently represent integers from 0 to 4.

11. The method for manufacturing a semiconductor package according to claim 10, wherein, X in equation (4-1) 1 and Y 1 Each is an organic group that independently contains a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4), wherein X in formula (4-2) 1 and Y 1 Each of these can be independently an organic group containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4). [Chemical Formula 5] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group. In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

12. The method for manufacturing a semiconductor package according to any one of claims 9 to 11, wherein, The negative photosensitive resin composition contains an oxime initiator.

13. The method for manufacturing a semiconductor package according to any one of claims 9 to 11, wherein, The negative photosensitive resin composition contains a polymeric compound having two or more olefinic unsaturated bonds.

14. The method for manufacturing a semiconductor package according to any one of claims 9 to 11, wherein, In the process of forming the rewiring layer A, the photosensitive film formed from the negative photosensitive resin composition is exposed using an i-ray stepper.

15. The method for manufacturing a semiconductor package according to claim 14, wherein, The numerical aperture of the i-ray stepper is 0.10 to 0.

60.

16. The method for manufacturing a semiconductor package according to claim 14, wherein, The exposure illuminance of the i-ray stepper is 500 W / m². 2 ~50000W / m 2 .

17. The method for manufacturing a semiconductor package according to claim 14, wherein, The exposure dose using the i-ray stepper is 1 mJ / cm. 2 ~2000mJ / cm 2 .

18. The method for manufacturing a semiconductor package according to any one of claims 8 to 11, wherein, The through-hole structure is formed by using a solvent as a developing solution.

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