Resin composition for substrate bonding, production method for laminate, and production method for semiconductor device

Abstract

Provided is a resin composition for substrate bonding that includes a resin that includes at least one of a polyimide precursor and a polyimide, the resin content being at least 50 mass% of the total solid content of the resin composition. When the resin composition is applied to a surface of a first substrate that has steps that have a height of 10 μm from the surface of the first substrate to form a resin film and a second substrate that does not have steps is brought into contact with the resin film and bonded by heat and pressure, the peeling strength between the first substrate and the second substrate is at least 10 J / m2. Also provided are a production method for a laminate and a production method for a semiconductor device.

Description

Resin composition for bonding substrates, method for manufacturing laminates, and method for manufacturing semiconductor devices

[0001] The present invention relates to a resin composition for bonding substrates, a method for manufacturing laminates, and a method for manufacturing semiconductor devices.

[0002] In modern times, with the miniaturization and performance improvement of semiconductor devices, three-dimensional stacking of multiple semiconductor substrates is being considered. In such stacking, a resin composition containing an insulating resin is applied to at least one substrate to form a resin composition layer, and other substrates are stacked on this resin composition layer and bonded together to manufacture the laminate.

[0003] For example, Patent Document 1 describes a curable resin composition containing an organosilicon compound and a solvent, wherein the viscosity at 25°C is 2000 cP or less, the solvent content in the curable resin composition is 50% by weight or less, and the adhesion of a measurement sample obtained by spin-coating on a silicon wafer, drying the solvent, and then thermal curing at 300°C for 1 hour is 0 to 2 points as measured by the cross-cut method in accordance with JIS K5600-5-6.

[0004] Japanese Patent Publication No. 2024-042696

[0005] Here, in the manufacturing of laminates by joining as described above, there is a need to improve the yield when the laminate is diced into individual pieces. A good yield when diced means that the occurrence of chipping due to dicing is suppressed. Chipping refers to the chipping that occurs on the edge of the cutting line during dicing.

[0006] The present invention aims to provide a resin composition for bonding substrates that yields a laminate with excellent yield when diced, a method for manufacturing the laminate, and a method for manufacturing a semiconductor device including the method for manufacturing the laminate.

[0007] Examples of typical embodiments of the present invention are shown below. <1> A resin composition comprising a resin containing at least one of a polyimide precursor and polyimide, wherein the content of the resin is 50% by mass or more relative to the total solid content of the resin composition, and the resin composition is applied to the stepped surface of a first substrate having a step of 10 μm in height from the surface of the first substrate, a resin film is obtained by forming a film, and when the resin film is brought into contact with a second substrate without a step and bonded by heating and pressurizing, the peel strength between the first substrate and the second substrate is 10 J / m ２ The above-mentioned resin composition for bonding substrates. <2> The resin composition for bonding substrates according to <1>, wherein the difference between the maximum and minimum values ​​of the film surface height on the surface opposite to the first substrate of the resin film formed on the first substrate is less than 1 μm. <3> The resin composition for bonding substrates according to <1> or <2>, wherein the imidization rate of the resin is 95% or more. <4> The resin composition for bonding substrates according to any one of <1> to <3>, further comprising a surfactant. <5> The resin composition for bonding substrates according to any one of <1> to <4>, wherein the elastic modulus of the resin film is 50 MPa or less when the temperature is the same as the temperature at which bonding is performed. <6> The steps of forming a resin film by applying a resin composition containing a polyimide precursor and a resin containing at least one of polyimide, and a solvent, to the stepped surface of a first substrate having a step of 5 μm or more and 50 μm or less, and forming a film; and joining a second substrate to the resin film by bringing it into contact with the resin film, wherein the peel strength between the first substrate and the second substrate is 10 J / m ２ A method for manufacturing a laminate, comprising the step of obtaining a bonded body as described above. <7> The method for manufacturing a laminate according to <6>, wherein the resin composition contains 50% by mass or more of the resin with respect to the total solid content of the resin composition. <8> The method for manufacturing a laminate according to <6> or <7>, further comprising a polishing step of polishing the surface of the resin film by a chemical mechanical polishing method after the step of forming the resin film and before the step of obtaining the bonded body. <9> The method further comprising a step of heating the bonded body at a temperature of 200°C to 400°C after the step of obtaining the bonded body, wherein the peel strength after heating is 10 J / m ２The method for manufacturing a laminate according to any one of <6> to <8>. <10> The method for manufacturing a laminate according to any one of <6> to <9>, wherein the step on the first substrate is a step formed by a semiconductor chip. <11> The method for manufacturing a laminate according to any one of <6> to <10>, comprising the step of applying a resin composition containing a polyimide precursor and a resin containing at least one of polyimide, and a solvent, to a second substrate before the bonding step to form a second resin film, and in the step of obtaining the bonded body, the second resin film on the second substrate and the resin film are brought into contact and bonded. <12> The method for manufacturing a laminate according to <9>, wherein the step of forming the resin film includes a step of heating the composition film, and the heating temperature in the step of heating the composition film is higher than the heating temperature in the step of heating the bonded body. <13> A method for manufacturing a semiconductor device, comprising the method for manufacturing a laminate according to any one of <6> to <12>.

[0008] The present invention provides a resin composition for bonding substrates that yields a laminate with excellent yield when diced, a method for manufacturing the laminate, and a method for manufacturing a semiconductor device including the method for manufacturing the laminate.

[0009] Figure 1 is a schematic plan view of a first substrate having a step on a silicon substrate. A schematic cross-sectional view shows a state in which a blade is inserted into the bonding interface between the bonded first and second substrates. A schematic cross-sectional view shows an example of a method for manufacturing a laminate according to the present invention.

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, preferred embodiments are more preferred embodiments.

[0011] (Resin composition for bonding substrates) The resin composition for bonding substrates of the present invention (hereinafter also simply referred to as "resin composition") is a resin composition comprising a polyimide precursor and a resin comprising at least one of polyimide, wherein the content of the resin is 50% by mass or more relative to the total solid content of the resin composition, and when the resin composition is applied to the surface of a first substrate having a step of 10 μm in height from the surface of the first substrate, a resin film is obtained by forming a film, and when the resin film is brought into contact with a second substrate without a step and bonded by heating and pressurizing, the peel strength between the first substrate and the second substrate is 10 J / m ２ That's all.

[0012] In the manufacturing of semiconductor devices, for example, a substrate such as a wafer is bonded to another substrate such as a chip, and then the device is diced to form individual pieces. However, during this dicing process, delamination or misalignment may occur at the bonded joints, sometimes resulting in poor yield. The inventors of the present invention have found that using the substrate bonding resin composition of the present invention for the bonding process significantly improves the yield. This improved yield has the advantage of enabling the production of packages at a low cost without wasting expensive chips. The mechanism by which the above effect is achieved is unknown, but it is presumed to be as follows.

[0013] The resin composition for bonding substrates of the present invention results in a cured product containing 50% or more by mass of polyimide after bonding. This polyimide exhibits excellent mechanical properties such as elongation at break and Young's modulus. Therefore, the resulting cured product also exhibits excellent mechanical properties, and it is believed that the bonding between the first and second substrates will be maintained even if deformation and stress concentration occur during dicing. Furthermore, the peel strength between the first and second substrates is 10 J / m ２ Therefore, it is believed that delamination during dicing is suppressed. Furthermore, polyimide is a material with excellent heat resistance and a high glass transition temperature. For this reason, it is expected to have excellent peel strength after the heat treatment described later, and also to have excellent handling properties even under high-temperature conditions.

[0014] Patent Document 1 does not describe or suggest such a resin composition for substrate bonding. Hereinafter, the resin composition of the present invention will be described in detail.

[0015] <Peeling Strength> When the resin composition of the present invention is applied to the surface of a first substrate having a step with a height of 10 μm from the surface of the first substrate, formed into a film to obtain a resin film, and a second substrate having no step is brought into contact with the resin film and bonded by heating and pressing, the peeling strength between the first substrate and the second substrate is 10 J / m ２ or more.

[0016] The peeling strength is preferably 12 J / m ２ or more, and more preferably 15 J / m ２ or more. The upper limit of the peeling strength is not particularly limited. For example, it is preferably 100 J / m ２ or less.

[0017] As the first substrate, a substrate having a step shown in FIG. 1 is used. FIG. 1 is a schematic plan view of a first substrate 100 having a step 104 on a substrate 102 formed of silicon. The step height is 10 μm, the step width d1 is 5 cm, the step interval d2 is 300 μm, the width d3 of the substrate is 200 mm, and the thickness is 500 μm. Also, the TTV (Total Thickness Variation) of the surface of the substrate having a step is 12 μm. In this specification, the drawings are merely schematic diagrams for explanation, and the shapes, scales, etc. of each element in the drawings may be different from the actual ones.

[0018] As a method for applying the resin composition of the present invention to a stepped surface of a first substrate, a spin coating method is used. After coating to a thickness of 30 μm, the wafer edge is removed by extruding cyclopentanone solution to remove 10 mm from the wafer edge, and then baking is performed at 100°C for 5 min. The above baking is performed using a hot plate. If a thickness of 30 μm cannot be achieved by the spin coating method, other methods such as the slit coating method may be used. Furthermore, the temperature and time of the above baking may be appropriately adjusted considering the conditions for removing the solvent from the resin composition. In addition, if drying is unnecessary, such as when the resin composition does not contain solvent, the above baking may be omitted. The film formation is performed at 350°C for 1 hour. ２ This is done by heating under controlled conditions.

[0019] As the second substrate, a substrate made of silicon is used, having a surface TTV of 2 μm, a substrate width of 200 mm, and a substrate thickness of 500 μm, and having no steps. In this specification, "having no steps" means not having steps of 1 μm or more in height. In this specification, "step" means a part in which the height increases or decreases by 1 μm or more within a width of 1 μm or less.

[0020] The heating and pressurizing in the above-mentioned bonding are carried out under a vacuum of 0.005 bar (wherein in this invention 1 bar is 10.1972 MPa), with bonding conditions of a bonding temperature of 300°C, a pressurizing force of 21,000 N, and a bonding time of 10 minutes.

[0021] The above peel strength is measured by the blade insertion method. The blade insertion method is a method of evaluating the strength of the joint as surface energy from the blade tip when a blade is inserted into the joint interface, as shown in Figure 2. Figure 2 is a schematic cross-sectional view showing the state in which a blade 114 is inserted into the joint interface of a first substrate 110 and a second substrate 112 that have been joined. In Figure 2, a blade 114 with a thickness h is inserted into the joint interface of the first substrate 110 with a thickness t1 and the second substrate 112 with a thickness t2. In Figure 2, a resin film actually exists between the first substrate 110 and the second substrate 112, but it has been omitted from the description. Due to the insertion of the blade, peeling occurs from the blade tip over a peel length L. The surface energy γ is calculated using the above peel length L by the following formula (1). Here, γ １ γ is the surface energy of the first substrate side, ２ E is the surface energy of the second substrate side. １ The Young's modulus of the first substrate is E. ２ The Young's modulus of the second substrate is t. １ The thickness of the first substrate is t. ２ is the thickness of the second base material, and h is the thickness of the blade.

[0022] <Flatness> The difference between the maximum and minimum values ​​of the film surface height on the surface opposite to the first substrate of the resin film formed on the first substrate (flatness) is preferably less than 1 μm, more preferably less than 0.5 μm, even more preferably less than 0.2 μm, and particularly preferably less than 0.1 μm. The flatness is preferably 0.005 μm or more. The method for forming the first substrate and resin film is the same as the method for forming the first substrate and resin film described in "Peel Strength" above.

[0023] <Peel strength after polishing> When the resin film formed on the first substrate is further subjected to a chemical polishing process before bonding with the second substrate, the peel strength of the bonded body is 10 J / m ２ Preferably, it is 12 J / m ２ Preferably, it is 15 J / m ２ It is more preferable that the above values ​​are met. The upper limit of the peel strength is not particularly limited, for example, 100 J / m２ The following is preferable. The method for forming the first substrate and resin film is the same as the method for forming the first substrate and resin film described in "Peel Strength" above. The chemical polishing process is carried out using CMP (Chemical Mechanical Polishing) manufactured by Fujikoshi Machinery Industries, Ltd. The chemical polishing process can be carried out using an alumina slurry (Polifine A100-Type MX manufactured by Kemet Japan), with a polishing pressure of 3 psi and a polishing time of 6 min. Furthermore, the method for joining the first substrate and the second substrate after the chemical polishing process is the same as the joining method described in "Peel Strength" above.

[0024] <Module of Elasticity> When the temperature is the same as the temperature at which the above bonding takes place, the modulus of elasticity of the resin film is preferably 50 MPa or less, more preferably 45 MPa or less, and even more preferably 30 MPa or less. The lower limit of the above modulus of elasticity is not particularly limited, but it is preferably 0.1 MPa or more. Furthermore, a modulus of elasticity of 10 MPa or less is also one of the preferred embodiments of the present invention. In the above embodiment, a modulus of elasticity of 5 MPa or less is even more preferred. The above resin film is obtained by forming a resin film on the first substrate described in "Peel Strength" above using the resin film formation method described in "Peel Strength" above, and then immersing the first substrate and the resin film in a 4.9 mass% hydrofluoric acid solution. The above modulus of elasticity is calculated by performing DMA measurement (dynamic mechanical measurement) on the resin film after peeling from room temperature to 400°C.

[0025] <Specific Resin> The resin composition of the present invention comprises a resin (specific resin) selected from the group consisting of polyimide precursors and polyimides.

[0026] The content of the specific resin in the resin composition of the present invention is 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 90% by mass or less, and more preferably 80% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0027] From the viewpoint of suppressing shrinkage during curing, the resin composition of the present invention preferably contains polyimide. By suppressing shrinkage during curing, it may be possible to omit polishing the resin layer before bonding, or to reduce the amount of polishing. In this specification, polyimide refers to a resin having repeating units containing imide structures in its molecular chain, and it is preferable that the resin has repeating units containing imide ring structures in its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide structures in its main chain, and it is more preferable that the resin has repeating units containing imide ring structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. In this specification, imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, and it is preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, an imide ring structure refers to a ring structure that includes all two carbon atoms and nitrogen atoms in the above-described imide structure as ring members. The imide ring structure is preferably a five-membered ring. In addition to the imide structure, the polyimide may also be a so-called polyamide imide, which has an amide structure in its molecular chain. In this specification, an amide bond refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0028] In the present invention, a polyimide precursor refers to a resin that undergoes a change in chemical structure due to external stimuli to become a polyimide. A resin that undergoes a change in chemical structure due to heat to become a polyimide is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyimide is more preferred. The preferred embodiments of the formed polyimide are as described above.

[0029] The imidization rate (also called the "ring closure rate") of the specific resin is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. The upper limit of the above imidization rate is not particularly limited and may be 100% or less. Furthermore, if the specific resin is polyimide, the content of the imide structure in the specific resin is preferably 3 mmol / g or less, and more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, but for example, it can be 0.5 mmol / g or more.

[0030] In this invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Other solvents that can be used include solvents contained in the resin composition, such as NMP. The viscosity may also be changed as appropriate within an adjustable range. The silicon wafer to which the obtained resin layer has been applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm after film formation on the silicon wafer. Here, if only a resin solution with low viscosity can be obtained, and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be changed as appropriate. For example, if the film thickness is 5 μm or more, a similar value for the imidization rate can be obtained. The above resin layer was measured using the ATR method with Nicoleti S20 (manufactured by Thermofisher), with a measurement range of 4000-700 cm. －１ The measurement was taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１The imidization index A of the resin is calculated by dividing the value by the peak height of the peak with the maximum peak intensity (if there are multiple peaks) and heating the film at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min. The imidization index B is calculated in the same manner and the value obtained by dividing the imidization index A by the imidization index B is calculated as the imidization rate of the resin. In measuring the imidization rate, the resin to be measured for imidization rate can be obtained from the composition by, for example, the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water and crystallized to precipitate the resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours to obtain the resin.

[0031] [Polymerizable Groups] It is preferable that the specific resin has polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, etc., with groups having ethylenically unsaturated bonds being preferred. Examples of the above-mentioned groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, (meth)acrylamide groups, etc. Among these, (meth)acryloxy groups, (meth)acrylamide groups, vinylphenyl groups, or maleimide groups are preferred, and from the viewpoint of reactivity, (meth)acryloyl groups are more preferred. Furthermore, from the viewpoint of reducing the dielectric loss tangent, vinylphenyl groups or maleimide groups are preferred. In addition, radical polymerizable groups are preferred as polymerizable groups.

[0032] The polymerizable value (polymerizability value) relative to the total mass of a particular resin is preferably 0.2 to 5.0 mmol / g, more preferably 0.25 to 4.0 mmol / g, and even more preferably 0.3 to 3.0 mmol / g. In this specification, the polymerizability value is defined as the molar amount of polymerizable groups contained in 1 mole of the compound divided by the number-average molecular weight of the compound.

[0033] [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in terms of type, but it is preferable that it contains repeating units represented by the following formula (2). In formula (2), A１ and A ２ Each of these is independently an oxygen atom or -NR ｚ - represents R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R ｚ represents a hydrogen atom or a monovalent organic group.

[0034] A in equation (2) １ and A ２ Each of these is independently an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred. ｚ R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. １１１ R represents a divalent organic group. １１１ It is preferable that the base is one of the bases described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421.

[0035] Also, R １１１ From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51) In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R ５０ ~R ５７ At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). In formula (61), R ５８ and R ５９Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0036] R in equation (2) １１５ * represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure. In formula (5), R １１２ The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ It is more preferable that the group is selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0037] R １１５ Preferably, this is a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of Japanese Patent Publication No. 2023-003421.

[0038] In equation (2), R １１１ and R １１５It is also possible that at least one of them has an OH group. More specifically, R １１１ Examples include residues of bisaminophenol derivatives.

[0039] R in equation (2) １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R １１３ and R １１４ It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. １１３ and R １１４ It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups of the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0040]

[0041] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２- represents a cycloalkylene group or a polyalkylene oxy group. Preferred R ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -Polyalkylene oxy groups are examples, including alkylene groups such as ethylene groups and propylene groups, and -CH ２ CH(OH)CH ２-, cyclohexyl groups, polyalkylene oxy groups are more preferred, alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc. The number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0042] In equation (2), R １１３If R is a hydrogen atom, １１４ If the atom is a hydrogen atom, the polyimide precursor may form a pair salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0043] In equation (2), R １１３ and R １１４ At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0044] The polyimide precursor may also preferably contain 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.

[0045] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0046] The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude. Formula (2-A) In the formula (2-A), A １ and A ２ represent an oxygen atom, and R １１１ and R １１２ each independently represent a divalent organic group, and R １１３ and R １１４ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R １１３ and R １１４ is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

[0047] A １ 、A ２ 、R １１１ 、R １１３ and R １１４ are each independently the same as A １ 、A ２ 、R １１１ 、R １１３ and R １１４ in the formula (2), and the preferable ranges are also the same. R １１２ is the same as R １１２ in the formula (5), and the preferable ranges are also the same.

[0048] The polyimide precursor may contain one kind of the repeating unit represented by the formula (2), or may contain two or more kinds. Further, it may contain a structural isomer of the repeating unit represented by the formula (2). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit of the above formula (2).

[0049] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0050] 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. The molecular weight dispersion of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight. When a resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0051] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyimide means a polyimide that dissolves at 23°C in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium, and from the viewpoint of pattern formation, it is preferable that the polyimide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. From the viewpoint of film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0052] -Fluorine Atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have fluorine atoms. Fluorine atoms are, for example, in the R of the repeating unit represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0053] -Silicon Atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３１ It is more preferable that the silicon atoms or the organically modified (poly)siloxane structure described later be included. The silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and preferably 20% by mass or less.

[0054] - Ethylene-unsaturated bond - From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in the side chains, but it is preferable that it has one in the side chains. It is preferable that the above ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３２ or R １３１ Preferably, it is included in R １３２ or R １３１ It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in R １３１ It is more preferable that the group contains an ethylenically unsaturated bond. Examples of groups containing an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups containing a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0055]

[0056] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0057] In formula (IV), R ２１ This is an alkylene group having 2 to 12 carbon atoms, -O-CH ２ CH(OH)CH ２The characters represent -, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3; the repeating number of the alkylene oxy group preferably has 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0058] Among these, R ２１ It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1). In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group having two or more of these bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). ２１ This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), a preferred embodiment of L is an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms, as shown in formula (IV) R ２１The preferred embodiment is the same as that of an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * is the same as * in formula (IV), and the preferred embodiment is the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0059] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0060] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0061] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds. Examples of polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (4) described later. １３１ It is preferable that it be included in the following. The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0062] -Polarity-Converting Group- Polyimides may have polarity-converting groups such as acid-degradable groups. The acid-degradable group in polyimides is R in formula (2) above. １１３ and R １１４ The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity-converting group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ It is found at the ends of polyimides, etc.

[0063] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of 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. The above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. When polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development"), the acid value of 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. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid groups contained in polyimides are preferably acid groups with a pKa of 0 to 10, and more preferably acid groups with a pKa of 3 to 8. pKa is the negative common logarithm of the equilibrium constant Ka, considering the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is the value calculated by ACD / ChemSketch®. The value of pKa may also be referenced from the value published in the "Revised 5th Edition Chemical Handbook Basic Edition" edited by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. As such acid groups, polyimides preferably contain at least one selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and more preferably contain phenolic hydroxyl groups.

[0064] -Phenolenic Hydroxyl Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. １３２ or R １３１ It is preferable that it be included in [the polyimide]. The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0065] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4). In formula (4), R １３１ represents a divalent organic group, R １３２ R represents a tetravalent organic group. If it has a polymerizable group, the polymerizable group is R １３１ and R １３２ It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) In formula (4-1), R １３３ This is a polymerizable group, and the other groups are equivalent to those in formula (4). Formula (4-2) In formula (4-2), R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

[0066] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. １３１ R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is １１１ Similar examples are given, and the preferred range is also similar. １３１Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. １１１ Examples include:

[0067] R １３１ It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

[0068] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0069] Also, R １３１ It is preferable that the structure includes a group represented by formula (Y-1), and more preferably that it is a structure represented by formula (Y-1). In formula (Y-1), R １ and R ２ Each of the symbols independently represents a group having an ethylenically unsaturated bond, L represents a single bond or a divalent linking group that does not contain an imide bond, and * represents a bonding site with another structure.

[0070] In formula (Y-1), R １ and R ２ Each of these is preferably an independent group represented by the following formula (R1-1). In formula (R1-1), L Ｒ１represents an n+1 valent linking group, R Ｒ１ Each of these independently represents an aromatic group, maleimide group, (meth)acryloxy group, or (meth)acrylamide group directly bonded to a vinyl group, n represents an integer from 1 to 10, and * represents A in formula (A-2). １ Or A ２ This represents the bonding site with R. Ｒ１ Each of these groups is preferably an aromatic group or a maleimide group directly bonded to a vinyl group, and more preferably a vinylphenyl group. Ｒ１ is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ It is preferably a group represented by bonding with at least one group selected from the group consisting of -, a hydrocarbon group, * １ -C(=O)-L Ｒ２ - * ２ Or, * １ -C(=O)NR Ｎ -L Ｒ２ - * ２ It is preferable that the group is represented by the above L. Ｒ１ The hydrocarbon group in is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. Ｒ２ R represents a hydrocarbon group, preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms. Ｎ Hydrogen atoms or hydrocarbon groups are preferred, hydrogen atoms or alkyl groups are more preferred, hydrogen atoms or methyl groups are even more preferred, and hydrogen atoms are particularly preferred. * １ is equivalent to * in equation (R1-1), and * ２ R in equation (R1-1) Ｒ１ This represents the bonding site with R. Ｒ１ If L is a vinylphenyl group, Ｒ１ It is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group. Ｒ１ If it is a maleimide group, L Ｒ１ is an alkylene group having 1 to 4 carbon atoms or * １-C(=O)-L Ｒ２ - * ２ It is preferable that the group is represented by R. Ｒ１ If L is a (meth)acryloxy group or a (meth)acrylamide group, Ｒ１ teeth* １ -C(=O)NR Ｎ -L Ｒ２ - * ２ It is preferable that the base is represented by . n is preferably an integer from 1 to 4, preferably 1 or 2, and more preferably 1.

[0071] In equation (Y-1), L is a single bond, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -S (=O) ２ - or 9,9-fluoroorangeyl group is preferred. Also, L is a single bond, -C(CH ３ ) ２ - or -C (CF ３ ) ２ -This embodiment is also one of the preferred embodiments of the present invention.

[0072] In equation (Y-1), * represents R in equation (4). １３１ It is preferable that this is the bonding site with the nitrogen atom to which it is bonded.

[0073] R １３２ R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is １１５ Similar examples are given, and the preferred range is also similar. For example, R １１５ The four bonders of the tetravalent organic group, as exemplified, bond with the four -C(=O)- parts in formula (4) to form a fused ring.

[0074] R １３２ Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor. １１５ Examples include: From the standpoint of the strength of the organic film, R １３２ It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0075] R １３１and R １３２ It is also preferable that at least one of them has an OH group. More specifically, R １３１ As examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples, R １３２ As such, (DAA-1) to (DAA-5) above can be cited as more preferred examples.

[0076] It is also preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0077] To improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0078] To improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-capturing agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, and 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-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0079] Polyimide is a material in which all repeating units are R １３１ and R １３２ The combination of R may include the repeating unit represented by the above formula (4), which is the same. １３１ and R １３２ The polyimide may contain repeating units represented by formula (4) above, which include two or more different combinations of elements. In addition to the repeating units represented by formula (4) above, the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (2) above.

[0080] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0081] 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 resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is particularly preferably 15,000 or more. 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. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyimide as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimide are treated as a single resin are each within the above range.

[0082] [Method for producing the specific resin] The specific resin can be synthesized, for example, by the method described in paragraphs 0134-0136 of International Publication No. 2022 / 145355, or by reference to that method. The above description is incorporated herein by reference. It may also be synthesized by reference to other known methods.

[0083] <Other Resins> The resin composition of the present invention may also contain other resins different from the specified resin described above (hereinafter also simply referred to as "other resins"). Examples of other resins include polybenzoxazole precursors, polybenzoxazolephenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and the like.

[0084] When the resin composition of the present invention contains other resins, the content of the other resins 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, based on the total solid content of the resin composition. In the resin composition of the present invention, the content of other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. In one preferred embodiment of the resin composition of the present invention, the content of other resins is also low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0085] <Polymerizable Compounds> The resin composition of the present invention preferably contains polymerizable compounds. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0086] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0087] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable that it has 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0088] The molecular weight of the 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 radical crosslinking agent is preferably 100 or more.

[0089] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products 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, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0090] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0091] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0092] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0093] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0094] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0095] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0096] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0097] As radical crosslinking agents, radical crosslinking agents having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") are also preferred. Examples of crosslinking agent U include compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0098] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-methyl-1,5-pentanediol diacrylate. Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition of the present invention.Preferably used as monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as 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-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0099] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition. 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.

[0100] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0101] [Other Crosslinking Agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by photosensitization with the photoacid generator or photobase generator described above, and more preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from the photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0102] [Polymerization Initiator] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator. Alternatively, the photopolymerization initiator may be a compound that generates polymerization initiator species upon heat. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0103] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0104] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and 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 arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0105] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0106] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0107] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0108] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0109] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0110] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0111] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0112] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0113]

[0114] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0115] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton may be used. These contents are incorporated herein by reference.

[0116] In addition, compounds described in paragraphs 0113 to 0117 of Japanese Patent Publication No. 2023-058585 may be used as photopolymerization initiators. This description is incorporated into the present specification.

[0117] If the resin composition contains a photopolymerization initiator, its content 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, based on the total solid content of the resin composition. The resin composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0118] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0119] If the resin composition contains a sensitizer, the sensitizer content 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, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0120] [Chain Transfer Agents] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0121] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0122] If the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0123] [Thermal Polymerization Initiator] The resin composition of the present invention may also preferably contain a thermal polymerization initiator. Examples of thermal polymerization initiators include thermal radical polymerization initiators. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction between the resin and the polymerizable compound can be advanced, thereby further improving solvent resistance.

[0124] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0125] If a thermal polymerization initiator is included, its content 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, based on the total solid content of the resin composition. The resin composition may contain only one type of thermal polymerization initiator or two or more types. If two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0126] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a polyimide precursor, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and thus good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs 0249-0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0127] Examples of base-generating agents include, but are not limited to, the following compounds.

[0128]

[0129] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0130] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0131] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0132] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0133] Furthermore, as a base-generating agent, it is preferable that the amino group is protected by a t-butoxycarbonyl group, from the viewpoint of storage stability and base generation by deprotection during curing.

[0134] Examples of amine compounds protected by a t-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, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol Luamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) Examples include, but are not limited to, ethers, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or its derivative is protected by a t-butoxycarbonyl group.

[0135] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0136] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0137] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-A Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-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-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0138] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl 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.

[0139] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0140] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0141] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0142] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0143] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0144] 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, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0145] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0146] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, 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 may be 100% by mass. The above content can be determined by considering the solubility of specific resins and other components contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0147] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0148] <Metal Adhesion Enhancers> The resin composition of the present invention preferably contains a metal adhesion enhancer from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion enhancers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0149] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0150]

[0151] 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-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1). In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercially available products can be used as such oligomer-type compounds, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0152] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0153] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0154] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0155] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0156] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol 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 tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0157] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0158] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the details of which are incorporated herein by reference.

[0159] Specific examples of migration inhibitors include the following compounds.

[0160]

[0161] When the resin composition of the present invention contains 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, based on the total solid content of the resin composition.

[0162] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0163] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0164] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide, and the like. This information is incorporated herein by reference.

[0165] If the resin composition of the present invention 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, based on the total solid content of the resin composition.

[0166] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0167] <Light Absorbers> The resin composition of the present invention may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0168] The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0169] [Surfactants] The resin composition of the present invention preferably contains a surfactant. Various surfactants can be used as the surfactant, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0170] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially fluidity) of the composition when it is prepared are further improved, the uniformity of the coating thickness and the liquid-saving properties can be further improved, and the ability of the composition to follow steps is increased. In other words, when forming a film using a coating solution containing a surfactant, the interfacial tension between the surface to be coated and the coating solution is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. As a result, air bubbles and other particles are less likely to be included in the stepped areas, and it is possible to more favorably form a uniform film with less thickness variation.

[0171] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0172] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition. This will be incorporated into the specification.

[0173] <Other Additives> The resin composition of the present invention may optionally contain various additives, such as higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are included, their total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0174] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0175] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0176] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0177] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0178] When considering the application of the resin composition of the present invention as a semiconductor material, 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, from the viewpoint of wiring corrosion. In particular, the halogen atoms present in the form of halogen ions are 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. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0179] Conventional containers can be used as containers for the resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0180] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0181] For the purpose of removing foreign matter such as dirt and fine particles from the resin composition of the present invention, filtration using a filter is preferable. As a filter, for example, the filter described in paragraph 0287 of International Publication No. 2023 / 190064 can be used. This description is incorporated herein by reference.

[0182] (Method for manufacturing a laminate) The method for manufacturing a laminate of the present invention comprises the steps of: applying a resin composition containing a polyimide precursor and a resin containing at least one of polyimide, and a solvent, to the stepped surface of a first substrate having a step of 5 μm to 50 μm to form a resin film (resin film formation step); and joining a second substrate to the resin film by bringing it into contact with the resin film, and achieving a peel strength of 10 J / m between the first substrate and the second substrate. ２ The process includes a step (joining step) to obtain the above-mentioned joined body.

[0183] <Resin Film Formation Process> The method for manufacturing the laminate of the present invention includes a step (resin film formation step) in which a resin composition containing a polyimide precursor and a resin containing at least one of polyimide, and a solvent is applied to the stepped surface of a first substrate having a step of 5 μm or more and 50 μm or less, and a film is formed to form a resin film.

[0184] [First Substrate] The shape of the first substrate is not particularly limited, but examples include polygonal flat plates, discs, polyhedrons, etc. The material of the first substrate is not particularly limited and is not restricted to semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, or electrode plate for plasma display panels (PDP). These substrates may have layers such as adhesion layers or oxide layers made of hexamethyldisilazane (HMDS), encapsulating material (epoxy molding compound: EMC), etc., on their surface. The first substrate may be a wafer or a chip, but being a wafer is one of the preferred embodiments of the present invention. In the present invention, a wafer refers to a substrate containing a semiconductor and is a concept that includes panels etc. formed by a plurality of semiconductor elements. In the present invention, a chip refers to an individual piece containing a semiconductor formed by dicing or the like, and may be a single-sided chip or a double-sided chip. In the present invention, a semiconductor fabrication substrate is particularly preferred, and a silicon substrate (silicon wafer) is more preferred.

[0185] The step of the first substrate is 5 μm or more and 50 μm or less, preferably 5 to 30 μm, and more preferably 5 to 20 μm. The step is preferably formed by semiconductor chips, wiring, electrodes, etc., and more preferably by semiconductor chips. The spacing of the step is preferably 10 to 2,000 μm, preferably 10 to 1,000 μm, and more preferably 20 to 500 μm. The shape of the step is cylindrical, prismatic, or other, but is not particularly limited, but is preferably rectangular prismatic. The angle between the side surface of the step of the first substrate and the surface of the first substrate is preferably 80 to 100°, and more preferably 85 to 95°.

[0186] The thickness of the first substrate is not particularly limited and can be selected according to the application, but is preferably 50 to 1,000 μm, and more preferably 100 to 500 μm.

[0187] [Resin Composition] It is preferable to use the resin composition of the present invention described above as the resin composition used in the resin film formation process. In the resin composition used in the resin film formation process, the content of the specific resin is not limited, but it is preferable that the resin is contained in an amount of 50% by mass or more of the total solid content of the resin composition. The preferred embodiment of the content of the specific resin is as described above.

[0188] [Composition Film Formation Process] The resin film formation process may include a step of applying the resin composition to the stepped surface of the first substrate to obtain a composition film (composition film formation process). Specific examples of methods for applying the resin composition to the stepped surface of the first substrate include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the composition and the application conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the application method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be applied in which a coating film formed in advance on a temporary support using the above application method is transferred to the first substrate. For the transfer method, the manufacturing methods described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. Furthermore, a step of removing excess film at the edges of the first substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may be adopted in which various solvents are applied to the substrate before applying the composition to the first substrate to improve the wettability of the sealing layer before applying the composition.

[0189] [Drying Step] After the composition film formation step described above, the formed composition film may be subjected to a drying step (drying step) to remove the solvent. That is, the resin film formation step may include a drying step to dry the applied composition film. The drying temperature in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0190] [Exposure and Development Processes] If the resin composition contains a photopolymerization initiator, exposure and development may be performed on the composition film or the composition film after the drying process by known methods. For example, the resin composition can be removed from the areas that are cut during dicing (dicing lines). According to such embodiments, for example, contamination by foreign matter due to resin peeling during dicing can be prevented. As a result, the yield in the manufacture of the bonded body can be improved. Details of the exposure process, such as exposure means and exposure conditions, can be found in paragraphs 0027 to 0029 of Japanese Patent Application Publication No. 2023-178289. The above description is incorporated herein by reference. Details of the development process, such as developer, development method and development conditions, can be found in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2023-178289. The above description is incorporated herein by reference.

[0191] [Heating Step] The composition film applied to the first substrate by the above composition film formation step (which may have gone through a drying step, an exposure step, or a developing step) is preferably subjected to a heating step for heating the resin composition. That is, the resin film formation step may include a heating step for heating the composition film. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in the specific resin or crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 150 to 450°C, more preferably 180 to 400°C, even more preferably 200 to 380°C, and most preferably 230 to 360°C.

[0192] Furthermore, it is preferable that the heating temperature in the step of heating the composition film is lower than the heating temperature in the step of heating the bonded body, which will be described later. In the above embodiment, the temperature difference is preferably 10°C or more, more preferably 20°C or more, and even more preferably 30°C or more.

[0193] When the resin composition contains a polyimide precursor, the heating step is preferably a step in which heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

[0194] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out heating at a heating rate of 1 to 8°C / second from the initial heating temperature to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0195] The starting temperature for heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when the composition is applied to a substrate and then dried, this is the temperature of the film (layer) after drying, and it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the composition.

[0196] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0197] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0198] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably carried out for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes. The pretreatment process may consist of two or more steps; for example, the first pretreatment step may be carried out in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, the film may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0199] The heating process is preferably carried out in a low-oxygen atmosphere, such as by flowing an inert gas like nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0200] [Physical Properties of the Resin Film] The resin film obtained in the resin film formation process preferably has a difference (flatness) of less than 1 μm between the maximum and minimum values ​​of the film surface height on the surface opposite to the first substrate, more preferably less than 0.5 μm, even more preferably less than 0.2 μm, and particularly preferably less than 0.1 μm. The above flatness is preferably 0.005 μm or more.

[0201] <Polishing Step> The method for manufacturing a laminate of the present invention may further include a polishing step of polishing the surface of the resin film after the step of obtaining the resin film and before the step of obtaining the bonded body. Examples of polishing methods include chemical mechanical polishing (CMP) and physical polishing, but are not limited to these, and known methods can be used without particular restriction, and it is preferable to use chemical mechanical polishing. That is, the method for manufacturing a laminate of the present invention preferably further includes a polishing step of polishing the surface of the resin film by chemical mechanical polishing after the step of obtaining the resin film and before the step of obtaining the bonded body. By planarizing the surface of the resin film by the polishing step, the occurrence of voids and the like may be suppressed. The polishing rate of the resin film in the polishing step is preferably 100 nm / min or more, more preferably 200 nm / min or more, and even more preferably 400 nm / min or more. There is no particular upper limit to the polishing rate, but from the viewpoint of controlling the in-plane uniformity of the polished object, it is preferable to be less than 3000 nm / min. The slurry used in the above CMP is not particularly limited, but silica slurry, ceria slurry, alumina slurry, etc. can be used. For example, an alumina slurry is preferred from the viewpoint of flatness and polishing speed, and a silica slurry is preferred from the viewpoint of polishing speed. The particle size of the slurry is not particularly limited, but from the viewpoint of suppressing scratches, an average particle size of 1000 nm or less is preferred, an average particle size of 500 nm or less is more preferred, and an average particle size of 200 nm or less is even more preferred. The lower limit of the particle size of the slurry is not particularly limited, but from the viewpoint of polishing rate, it is preferred to be 10 nm or more. Alternatively, the process may be carried out by performing CMP after cutting. The polishing process can be carried out, for example, with a surface planer. Examples of surface planers include those with a diamond cutting tool attached to a spindle, such as the DFS8910, DFS8960, DAS8920, and DAS8930 (all trade names) manufactured by Disco.

[0202] <Bonding Process> The method for manufacturing the laminate of the present invention involves bringing a second substrate into contact with the resin film obtained in the resin film formation process (which may be further subjected to a polishing process if necessary) and bonding them, such that the peel strength between the first substrate and the second substrate is 10 J / m ２ The method for manufacturing a laminate of the present invention includes a step of obtaining the above-described bonded body (joining step). Here, the above-described bonded body may be obtained as a laminate, or the above-described bonded body may be subjected to other steps such as a heat-resistant treatment step described later and then obtained as a bonded body.

[0203] [Second Substrate] The material of the second substrate is not particularly limited and includes semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe; paper, SOG (Spin On Glass), TFT (thin-film transistor) array substrates, and electrode plates for plasma display panels (PDPs). These substrates may have layers such as adhesion layers or oxide layers made of hexamethyldisilazane (HMDS) or encapsulating materials (epoxy molding compound: EMC) on their surfaces. The second substrate may be in the form of a wafer or a panel. In the present invention, semiconductor manufacturing substrates are particularly preferred, and silicon substrates (silicon wafers) are more preferred.

[0204] The second substrate preferably does not have steps. A preferred embodiment when there are no steps is as described in the resin composition of the present invention above.

[0205] The thickness of the second substrate is not particularly limited and can be selected according to the application, but is preferably 50 to 1,000 μm, and more preferably 100 to 500 μm.

[0206] The second substrate may also preferably have a second resin film on its surface. In that case, it is preferable that the surface of the first substrate having the resin film and the surface of the second substrate having the second resin film are joined during the joining process. That is, the method for manufacturing the laminate of the present invention includes a step of applying a resin composition containing a polyimide precursor and a resin containing at least one of polyimide, as well as a solvent, to the second substrate to form a second resin film before the joining process, and in the step of obtaining the laminate, it is preferable to bring the second resin film of the second substrate into contact with the resin film and join them.

[0207] Preferred embodiments of the second resin film, the resin composition used to form the second resin film, and the method for forming the second resin film are the same as preferred embodiments of the first resin film, the resin composition used to form the first resin film, and the method for forming the first resin film.

[0208] [Joining Method] Joining is preferably carried out by means including heating, and more preferably by means including heating and pressurizing. The joining temperature is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 250°C or higher. The upper limit is preferably 450°C or lower, more preferably 400°C or lower, even more preferably 380°C or lower, and particularly preferably 350°C or lower. The heating time in the joining process is not particularly limited, but is preferably 5 seconds or more, more preferably 1 minute or more, and even more preferably 2 minutes or more. The upper limit is practically 30 minutes or less. The heating environment is not particularly limited, but is preferably carried out under a reduced pressure atmosphere while mechanically pressurizing the resin film. The atmospheric pressure is 1 × 10⁻⁶ －５ It is preferable that it be 1 × 10⁻¹⁰ mbar or higher. －４ It is more preferable that it be 5 × 10 mbar or higher. －４ It is even more preferable that it be 0 mbar or higher. Preferably, the upper limit is 0.1 mbar or less, and 1 × 10 －２ It is more preferable that it be less than or equal to mbar, and 5 × 10 －３It is even more preferable that the pressure be less than or equal to mbar. The bonding is preferably carried out by sandwiching two substrates (a first substrate and a second substrate), and it is preferable to apply pressure to the substrates at this time. The pressure applied to the substrates is preferably 1 kN or more, more preferably 5 kN or more, and even more preferably 10 kN or more. As an upper limit, it is practical to be 100 kN or less. The apparatus used in the bonding process is not particularly limited, and known wafer bonders and the like can be used.

[0209] [Peel Strength] The peel strength between the first substrate and the second substrate in the joint obtained by the above joining process is 10 J / m ２ That is all. 12 J / m ２ Preferably, it is 15 J / m ２ It is more preferable that the above values ​​are met. The upper limit of the peel strength is not particularly limited, for example, 100 J / m ２ The following is preferable. Here, the peeling strength is determined by measuring the amount of peeling using the blade insertion method described above, and adding E to the formula (1) described above. １ : Young's modulus of the first substrate, E ２ : Young's modulus of the second substrate, t １ : Thickness of the first substrate, t ２ This is calculated by substituting the following values: : thickness of the second substrate, h: blade thickness, and L: measured peeling amount.

[0210] <Heat-resistant treatment process> The method for manufacturing a laminate of the present invention further includes a step of heating the bonded body at a temperature of 200°C to 400°C after the step of obtaining the bonded body, wherein the peel strength after the above heating is 10 J / m ２ That is all. 12 J / m ２ Preferably, it is 15 J / m ２ It is more preferable that the above values ​​are met. The upper limit of the peel strength is not particularly limited, for example, 100 J / m ２ The following is preferable:

[0211] The heating temperature is preferably 220 to 400°C, and more preferably 240 to 400°C. Other heating conditions besides the heating method and temperature are not particularly limited and can be carried out, for example, by the method described in the heating process above.

[0212] The above peeling strength is determined by measuring the amount of peeling using the blade insertion method described above, and applying E to the above formula (1). １ : Young's modulus of the first substrate, E ２ : Young's modulus of the second substrate, t １ : Thickness of the first substrate, t ２ This is calculated by substituting the following values: : thickness of the second substrate, h: blade thickness, and L: measured peeling amount.

[0213] <Dicing Process> The manufacturing method of the laminate of the present invention may include a dicing process in which the bonded body is diced to obtain chips. In the dicing process, the bonded body is cut to a predetermined size. The dicing means is not particularly limited, and any known dicing means may be used, but a cutting method called full cut, in which the cut is made up to the dicing tape, a method in which the semiconductor wafer is partially cut and then divided by mechanical means after cooling, a laser cutting method, etc. can be employed.

[0214] <Other steps> The method for manufacturing the laminate of the present invention may include other steps known in the art without particular limitation.

[0215] <Example of a method for manufacturing a laminate> Figure 3 is a schematic cross-sectional view showing an example of a method for manufacturing a laminate according to the present invention. Figure 3(a) shows a first substrate 10 on which steps 14 are formed on a substrate 12. The height h1 of the steps 14 is 5 to 50 μm. The first substrate 10 may have wiring, electronic circuits, etc. on or within the substrate 12, and the wiring, electronic circuits, etc. may be electrically connected to, for example, semiconductor chips that form the steps 14. In Figure 3(a), the height h1 of all the steps 14 is about the same, but there may be steps 14 of different heights.

[0216] In Figure 3(b), a resin film 16 is formed by applying a resin composition to the surface of the first substrate 10 having a step 14 and depositing a film. The resin film 16 is manufactured by the resin film formation process as described above. h2 indicates the film surface height of the resin film 16 on the surface opposite to the first substrate. For example, if the resin composition contains polyimide, shrinkage of the film during film formation is suppressed, so the difference between the film surface height h2 at the location where the step 14 exists and the film surface height h2 at the location where the step 14 does not exist becomes small. For example, if the difference between the maximum and minimum values ​​of this film surface height h2 (flatness) is less than 1 μm, the peel strength due to bonding tends to increase. The preferred embodiment of the flatness is as described above. The resin film 16 may also be subjected to polishing afterward. Polishing is performed, for example, by the polishing process described above. By polishing the resin film 16, the surface becomes flat and the peel strength increases.

[0217] Figure 3(c) is a schematic cross-sectional view showing a laminate obtained by bonding a second substrate 18 onto a resin film 16. Bonding is performed by the bonding process described above. Here, if the second substrate 18 has a second resin film, the second resin film and the resin film 16 may fuse together and become one. The bonded body shown in Figure 3(c) may subsequently be subjected to the heat-resistant treatment process described above. Subjecting it to the heat-resistant treatment process improves the bonding reliability.

[0218] Figure 3(d) shows the chips 20 that have been separated into individual pieces by the dicing process, which were manufactured in Figure 3(c). According to the manufacturing method of the laminate of the present invention, peeling of the joints during dicing is suppressed, so it can be said that a laminate with excellent yield when dicing is performed can be obtained.

[0219] (Method for Manufacturing Semiconductor Devices) The method for manufacturing semiconductor components of the present invention preferably includes, for example, the method for manufacturing a laminate of the present invention as a step, and more preferably includes the method for manufacturing a laminate of the present invention as a step, and further includes the step of mounting one or more other components on the laminate obtained by the method for manufacturing a laminate of the present invention. Examples of semiconductor components include graphic processing units, volatile memories such as DRAM (Dynamic Random Access Memory) and SRAM (Static Random Access Memory), non-volatile memories such as flash memory, RF chips, silicon photonics chips, MEMS (Micro Electro Mechanical Systems), and sensor chips, and can be selected according to the application.

[0220] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0221] <Synthesis of Resin> [Synthesis Example P-1: Synthesis of Resin P-1] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled and 16.12 g (135.5 mmol) of SOCl was added. ２The solution was added over 2 hours. Next, a solution of 12.74 g (60.0 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 2 hours while adjusting the temperature to a range of -5 to 0°C. The reaction mixture was allowed to react at 0°C for 1 hour, after which 70 g of ethanol was added and the mixture was stirred at room temperature for 1 hour. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was filtered out, stirred again in 4 liters of water for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure for 2 days. The weight-average molecular weight of this polyimide precursor (polymer P-2) was 29,000.

[0222] [Synthesis Example P-2: Synthesis of Resin P-2] 208.7 g (401 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 6.55 g (21.1 mmol) of 4,4'-oxydiphthalic anhydride, and 345 mL of N-methylpyrrolidone (NMP) were mixed in a 3 L flask. A solution of 25.0 g (116 mmol) of 3,3'-dihydroxybenzidine, 54.0 g (270 mmol) of 4,4'-diaminodiphenyl ether, and 8.19 g (75.0 mmol) of 4-aminophenol, pre-dissolved in 970 g of NMP, was added dropwise. After the dropwise addition was complete, 144 ml of toluene was added and the mixture was stirred at 180°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature. Then, 5.92 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 161 g (1055 mmol) of p-chloromethylstyrene, 175 g (1266 mmol) of potassium carbonate, 21.0 g (127 mmol) of potassium iodide, and 438 g of NMP were added, and the mixture was stirred at 90°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, diluted with 3500 ml of THF, and filtered by suction filtration. The filtrate was added dropwise to 8800 mL of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain resin (P-1) as a powder. The weight-average molecular weight of the obtained resin (P-1) was 24,600, and the number-average molecular weight was 9,900. Resin (P-1) is a resin having repeating units represented by the following formula (P-1). The structure of the repeating unit is: １ The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0223] [Synthesis Example P-3: Synthesis of Resin P-3] 15.0 g (48.4 mmol) of 4,4'-oxydiphthalic anhydride, 4.74 g (16.1 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride, 12.0 g (92.3 mmol) of 2-hydroxyethyl methacrylate, 4.67 g (39.5 mmol) of 2-isobutoxyethanol, 0.05 g of hydroquinone, 22.7 g of pyridine (287 mmol), and 75 g of digrime (diethylene glycol dimethyl ether) are mixed. The mixture is stirred at 60°C for 4 hours to produce a mixture of diesters of 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2-hydroxyethyl methacrylate, and 2-isobutoxyethanol. Next, the reaction mixture was cooled to -10°C, and while maintaining the temperature at -10±4°C, 16.14 g (134.1 mmol) of SOCl was added. ２After adding over 60 minutes, the reaction mixture is stirred at room temperature for 2 hours. Next, a solution of 12.06 g (56.8 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -5 to 0°C. Then, the reaction mixture is reacted at 15°C for 1 hour, after which 11.9 g of ethanol is added and the mixture is stirred at room temperature for 2 hours. After adding 0.05 g of hydroquinone, the reaction mixture is added dropwise to 2 liters of water over 1 hour while stirring at a rate of 400 rpm (revolutions per minute) to precipitate the polyimide precursor. The polyimide precursor is obtained by filtration, and the obtained polyimide precursor is dried under reduced pressure at 45°C for 1 day to obtain the crude polyimide precursor (P-1). The obtained crude is then dissolved in 270 g of tetrahydrofuran. The dissolution is added dropwise to 2 liters of water over 1 hour while stirring at a rate of 400 rpm (revolutions per minute) to precipitate the polyimide precursor. The polyimide precursor is obtained by filtration, and the obtained polyimide precursor is dried under reduced pressure at 45°C for 1 day to obtain polyimide precursor (P-1). The weight-average molecular weight of this polyimide precursor (P-1) is 23,000. ¹H-NMR confirms that the obtained polyimide precursor (P-1) is presumed to contain repeating units represented by the following formula (P-1). １ ¹H-NMR confirmed that the imidization rate of the polyimide precursor was 0% and the HEMA introduction rate was 70%.

[0224] [Synthesis Example P-4: Synthesis of Resin P-4] 7.07 g (22.79 mmol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 4.12 g (19.4 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine are dissolved in 30 g of N-methylpyrrolidone. The resulting solution is stirred at 30°C for 4 hours, then at room temperature overnight. After that, 9.45 g (45.0 mmol) of trifluoroacetic anhydride is added at room temperature, followed by 7.08 g (54.4 mmol) of 2-hydroxyethyl methacrylate, and the mixture is stirred at 45°C for 10 hours. The reaction mixture is added dropwise to distilled water, the precipitate is filtered off and collected, and the resin P-4 is obtained by drying under reduced pressure. The weight-average molecular weight of resin P-4 is 20,000. １ ¹H-NMR confirmed that the obtained polyimide precursor (P-4) is presumed to contain repeating units represented by the following formula (P-4). １ ¹H-NMR confirmed that the imidization rate of the polyimide precursor was 0% and the HEMA introduction rate was 70%.

[0225] [Synthesis Example P-6: Synthesis of Resin P-6] 26.9 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride and 3.9 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride are dissolved in 49 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 3.3 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 10.4 g of m-tolidine, and 0.9 g of p-aminophenol are dissolved in 148 g of NMP, and 21 mL of toluene is added. While maintaining a temperature below 40°C, the above diamine solution is added dropwise to the acid anhydride solution over 1 hour, and then the reaction is carried out at 200°C for 4 hours. During the reaction, reflux and dehydration are carried out using a Dean-Stark strainer. After the reaction is complete, the mixture is cooled to 25°C. To the above reaction solution, 0.90 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 26.3 g of 4-chloromethylstyrene, 28.6 g of potassium carbonate powder, 3.4 g of potassium iodide, and 66 g of NMP are added, and the mixture is reacted at 95°C for 2 hours. After the reaction is complete, the mixture is cooled to 25°C, diluted with 400 mL of tetrahydrofuran, solid matter is removed by filtration, and the mixture is then washed with 200 mL of tetrahydrofuran. Next, the reaction solution is added dropwise to a mixture of 2.0 liters of methanol and 0.9 L of water, stirred for 60 minutes, and then the polyimide resin is filtered. After filtration, the mixture is dried under reduced pressure at 40°C for 15 hours. Next, the dried resin is dissolved in 450 mL of tetrahydrofuran, and 0.23 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical is added and dissolved. Then, 66 g of ion exchange resin (MB-1: Organo Co., Ltd.) is added, and the mixture is stirred for 2 hours. After removing the ion exchange resin by filtration, the polyimide resin is precipitated in 2.0 liters of methanol and stirred for 60 minutes. The polyimide resin is obtained by filtration and dried under reduced pressure at 40°C for 20 hours to obtain 44.7 g of polyimide resin, resin P-6. The structural formula of resin P-6 is shown below. The weight-average molecular weight of resin P-6 is 28,000. １ The imidization rate of resin P-6 by H-NMR is 100%.

[0226] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed and pressure filtered using a polypropylene filter with a pore width of 0.45 μm to obtain each substrate bonding resin composition and a comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) indicated in the "parts by mass" column of each column in the table. In the table, "-" indicates that the composition does not contain the corresponding component.

[0227]

[0228] Details of each component listed in the table are as follows:

[0229] [Resins] ・Resins P-1 to P-4, P-6: Resins P-1 to P-4, P-6 synthesized as described above ・Resin P-5: PMMA (Polymethyl Methacrylate)

[0230] [Metal adhesion improvers] ・A-1 to A-4: Compounds with the following structure

[0231] [Polymerizable compounds] ・B-1: SR-209 (manufactured by Sartomer) ・B-2: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ・B-3: Compound with the following structure

[0232] [Polymerization Initiators] ・C-1: IRGACURE OXE01 (manufactured by BASF) ・C-2 to C-3: Compounds with the following structure

[0233] [Polymerization inhibitors] ・D-1: Compounds with the following structure

[0234] [Migration Inhibitors] ・E-1: Compounds with the following structure

[0235] [Base Generator] ・H-1: Compound with the following structure

[0236] [Surfactants] ・I-1: BYK-333 (Polyether-modified polydimethylsiloxane, manufactured by BYK Chemie)

[0237] [Solvents] J-1: γ-butyrolactone J-2: Dimethyl sulfoxide J-3: Cyclohexanone

[0238] <Evaluation> [Evaluation of composition properties] The following first and second substrates were prepared.

[0239] -First Substrate- This substrate has a step as shown in Figure 1. The material of the substrate and the step is silicon. The step width d1 is 300 μm, the substrate width d2 is 200 mm, and the thickness is 500 μm. The TTV (Total Thickness Variation) of the substrate surface is 12 μm.

[0240] -Second Substrate- The second substrate is a substrate made of silicon, with a TTV of 2 μm on the substrate surface, a substrate width of 200 mm, and a substrate thickness of 500 μm, and is a substrate without steps.

[0241] In each example or comparative example, each composition listed in the "Composition" column of "First Substrate" in the table was applied to the stepped surface of the first substrate to a thickness of 30 μm, the wafer edge was dissolved and removed by 10 mm with cyclopentanone solution, and the wafer was baked at 100°C for 5 min. Furthermore, it was subjected to N24 under conditions of 350°C for 1 hour. ２ The resin film was formed by heating under atmospheric conditions.

[0242] The surface of the resin film was planarized using CMP (Chemical Mechanical Polishing) manufactured by Fujikoshi Machinery Industries, Ltd. Alumina slurry (Polifine A100-Type MX manufactured by Kemet Japan) was used, and CMP was performed with a polishing pressure of 3 psi and a polishing time of 6 min.

[0243] The difference between the maximum and minimum values ​​of the film surface height (flatness) on the surface opposite to the first substrate of the resin film deposited on the first substrate was measured using an ellipsometer and recorded in the "Flatness [μm]" column of the table. The first substrate and the resin film were immersed in a 4.9 mass% hydrofluoric acid solution, and the cured material (test piece) was peeled off from the silicon wafer. DMA measurement (dynamic mechanical measurement) was performed from room temperature to 300°C, and the elastic modulus (E') at 300°C was obtained and recorded in the "Elastic Modulus [Mpa]" column of the table.

[0244] As described above, the first and second substrates, on which resin films were deposited, were bonded using an EVG wafer bonder. The bonding conditions were a bonding temperature of 300°C, a bonding pressure of 21,000 N, and a bonding time of 10 minutes.

[0245] The peel strength of the above-mentioned joint was evaluated using the blade insertion method. In the evaluation, the blade thickness h was set to 100 μm, the peel length L was set to the measured value mentioned above, and E was used in the above-mentioned formula (1). １ and E ２ t is the Young's modulus of a silicon wafer, which is 131 GPa. １ and t ２ The surface energy γ is calculated by substituting a silicon wafer thickness of 500 μm, and the peel strength (composition) (J / m) is calculated. ２ I wrote it in the section marked ")".

[0246]

[0247] [Manufacturing and Evaluation of Laminates] A first substrate and a second substrate similar to those used for characterizing the compositions described above were prepared. However, the material of the substrate and steps in the first substrate is the material described in the "Type" column of "First Substrate" in the table, and the step height is the height described in "Step Height / μm" in the table. Also, the material of the substrate and steps in the second substrate is the material described in the "Type" column of "Second Substrate" in the table.

[0248] In each example or comparative example, each composition listed in the "Composition" column of "First Substrate" in the table was applied to the first substrate to a thickness of 30 μm, the wafer edge was dissolved and removed by 10 mm with cyclopentanone solution, and the wafer was baked at 100°C for 5 min. Furthermore, under the film deposition temperature and film deposition time conditions listed in the "Film Deposition Temperature / °C" and "Film Deposition Time / hour" columns of "First Substrate" in the table, N ２The resin film was deposited by heating under atmospheric conditions. Subsequently, in the cases where "Yes" was indicated in the "CMP" column of "First Substrate" in the table, the surface of the polyimide-containing portion was flattened using CMP (Chemical Mechanical Polishing) manufactured by Fujikoshi Machinery Industries, Ltd. to achieve the flatness indicated in the table, thereby obtaining a substrate 1 with a polyimide-containing portion. In the cases where "Alumina" was indicated in the "Polishing Method" column of the table, an alumina slurry (Polifine A100-Type MX manufactured by Kemet Japan) was used, and in the cases where "Silica" was indicated, a silica slurry was used. The difference between the maximum and minimum values ​​of the film surface height on the surface of the deposited resin film opposite to the first substrate was measured using an ellipsometer and recorded in the "Flatness / μm" column of "First Substrate" in the table.

[0249] In each example or comparative example, each composition listed in the "Composition" column of "Second Substrate" in the table was applied to the second substrate to a thickness of 30 μm, the wafer edge was dissolved and removed by 10 mm with cyclopentanone solution, and the wafer was baked at 100°C for 5 min. Furthermore, under the film deposition temperature and film deposition time conditions listed in the "Film Deposition Temperature / °C" and "Film Deposition Time / hour" columns of "Second Substrate" in the table, N ２ The resin film was formed by heating under atmospheric conditions. Subsequently, in the cases where "alumina" or "silica" is listed under "Second Substrate" in the table, the surface of the polyimide-containing portion was then flattened using CMP (Chemical Mechanical Polishing) manufactured by Fujikoshi Machinery Industries, Ltd. to achieve the flatness indicated in the table, thereby obtaining a substrate 2 having a polyimide-containing portion. In the cases where "alumina" is listed in the "Polishing Method" column of the table, an alumina slurry (Polifine A100-Type MX manufactured by Kemet Japan) was used to flatten the surface of the polyimide-containing portion. ２ In the examples marked with "", FSL1531C (manufactured by FUJIFILM Electronic Materials) was used. In the examples where "-" is written in the "Composition" column of "Second Substrate" in the table, the second substrate was used as is for bonding as described below, without resin coating, film formation, or planarization.

[0250] - Manufacturing of Laminates - As described above, the first substrate and the second substrate, on which resin films were deposited, were joined using an EVG wafer bonder. The joining conditions were the "temperature," "pressure," "time," and "vacuum level" conditions listed in the "Joining Conditions" column of the table. The elastic modulus of the resin film deposited on the first substrate is also listed for the temperature specified in the "Temperature" column of the "Joining Conditions" column of the table. The elastic modulus (E') was obtained by immersing the first substrate and the resin film in a 4.9 mass% hydrofluoric acid solution, peeling the cured material (test piece) from the silicon wafer, and performing DMA measurement (dynamic mechanical measurement) from room temperature to 400°C. After joining, the joined members were heated at the temperature and time specified in the "Heat Resistance Treatment" column of the table to perform heat resistance treatment and obtain a laminate.

[0251] - Measurement of peel strength - The peel strength was evaluated using the blade insertion method described above for the member before the heat-resistant treatment and the laminate after the heat-resistant treatment described above. In the test, the blade thickness h was set to 100 μm, the peel length L was set to the measured value described above, and E was added to the formula (1) described above. １ and E ２ t is the Young's modulus of a silicon wafer, which is 131 GPa. １ and t ２ The above surface energy γ is calculated by substituting a silicon wafer thickness of 500 μm, and the peel strength (J / m) is calculated. ２ I wrote it in the section marked ")".

[0252] -Yield Evaluation- The back side of the first substrate of the laminate obtained in each example or comparative example was attached to a dicing tape, and blade dicing was performed along the stepped portion using a dicing machine to obtain 5 cm square chips. The number of chipped chips out of 10 chips obtained during dicing was counted, and the yield was evaluated. The evaluation was carried out according to the evaluation criteria below, and the evaluation results are recorded in the "Yield" column of the table. <<Evaluation Criteria>> A: The number of chipped chips was 0. B: The number of chipped chips was 2 or less. C: The number of chipped chips was 3 or more.

[0253]

[0254]

[0255] From the above results, it can be seen that using the resin composition for bonding substrates of the present invention results in excellent yield during dicing. In Comparative Examples 1 and 2, when the resin composition for bonding substrates is applied to the surface of a first substrate having a step of 10 μm in height from the surface of the first substrate, a resin film is formed, and a second substrate without a step is brought into contact with the resin film and bonded by heating and pressurizing, the peel strength between the first substrate and the second substrate is 10 J / m ２ It is less than [value missing]. It can be seen that when such a resin composition for bonding substrates is used, the yield in dicing decreases. Furthermore, it can be seen that the laminate obtained by the laminate manufacturing method of the present invention has excellent yield when subjected to dicing. The laminate obtained by the laminate manufacturing method according to Comparative Examples 1 and 2 has a peel strength of 10 J / m between the first substrate and the second substrate. ２ It is less than [amount missing]. It can be seen that the yield in dicing decreases when using such laminates.

[0256] 10 First substrate 12 Substrate 14 Step 16 Resin film 18 Second substrate 100 First substrate 102 Substrate 104 Step 110 First substrate 112 Second substrate 114 Blade d1 Step width d2 Substrate width h Blade thickness h1 Step height h2 Film surface height L Peel length

Claims

1. A resin composition comprising a resin containing at least one of a polyimide precursor and polyimide, wherein the resin content is 50% by mass or more relative to the total solid content of the resin composition, and when the resin composition is applied to the stepped surface of a first substrate having a step height of 10 μm from the surface of the first substrate, a resin film is obtained by forming a film, and when the resin film is brought into contact with a second substrate without a step and bonded by heating and pressurizing, the peel strength between the first substrate and the second substrate is 10 J / m ２ The above-mentioned resin composition for bonding substrates.

2. The resin composition for bonding substrates according to claim 1, wherein the difference between the maximum and minimum values ​​of the film surface height on the surface opposite to the first substrate of the resin film formed on the first substrate is less than 1 μm.

3. The resin composition for bonding substrates according to claim 1, wherein the imidization rate of the resin is 95% or more.

4. The resin composition for bonding substrates according to claim 1, further comprising a surfactant.

5. The resin composition for bonding substrates according to any one of claims 1 to 4, wherein the elastic modulus of the resin film is 50 MPa or less when the temperature is the same as the temperature at which bonding is performed.

6. A step of forming a resin film by applying a resin composition containing a polyimide precursor and a resin containing at least one of polyimide, and a solvent, to the stepped surface of a first substrate having a step of 5 μm or more and 50 μm or less, and forming a film; and a step of joining a second substrate to the resin film by bringing it into contact with the resin film, and having a peel strength of 10 J / m between the first substrate and the second substrate. ２ A method for manufacturing a laminate, comprising the step of obtaining a bonded body as described above.

7. The method for producing a laminate according to claim 6, wherein the resin composition contains 50% by mass or more of the resin with respect to the total solid content of the resin composition.

8. The method for manufacturing a laminate according to claim 6 or 7, further comprising a polishing step of polishing the surface of the resin film by a chemical mechanical polishing method after the step of forming the resin film and before the step of obtaining the bonded body.

9. The process further includes heating the bonded body at a temperature of 200°C to 400°C after obtaining the bonded body, wherein the peel strength after heating is 10 J / m ２ The method for manufacturing a laminate according to claim 6 or 7.

10. The method for manufacturing a laminate according to claim 6 or 7, wherein the step in the first substrate is a step formed by a semiconductor chip.

11. The method for manufacturing a laminate according to claim 6 or 7, comprising the step of applying a resin composition containing a polyimide precursor and a resin containing at least one of polyimide, and a solvent, to a second substrate before the bonding step to form a second resin film, and in the step of obtaining the laminate, the second resin film of the second substrate and the resin film are brought into contact and bonded.

12. The method for manufacturing a laminate according to claim 9, wherein the step of forming the resin film includes a step of heating the composition film, and the heating temperature in the step of heating the composition film is higher than the heating temperature in the step of heating the bonded body.

13. A method for manufacturing a semiconductor device, comprising the method for manufacturing a laminate according to claim 6 or 7.

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