Method for manufacturing semiconductor device, resin composition, and resin composition for temporary adhesive layer

Abstract

This method for manufacturing a semiconductor device includes: a step for preparing a substrate A; a temporary adhesive layer forming step for forming a temporary adhesive layer on one surface of the substrate A; a step for preparing a substrate B; a bonding step for bonding the surface of the substrate A having the temporary adhesive layer to the substrate B; and a peeling step for peeling the substrate A from the substrate B by irradiation with a laser. The temporary adhesive layer is formed of a resin composition containing a polyamic acid ester.

Description

Method for manufacturing semiconductor devices, resin composition, and resin composition for temporary adhesive layer

[0001] The present invention relates to a method for manufacturing semiconductor devices, a resin composition, and a resin composition for a temporary adhesive layer.

[0002] In semiconductor device manufacturing methods, various resins are known to be used in temporary bonding resin compositions used in the temporary bonding process, or in other words, the TBDB (Temporary bonding de-bonding) process. For example, polyimide, which has excellent heat resistance and elastic modulus, is used (Patent Document 1). Polyamic acid is also known as a resin used in temporary bonding resin compositions (Patent Document 2).

[0003] International Publication No. 2024 / 58061, Japanese Patent Publication No. 2017-530206

[0004] In the TBDB process, substrates such as silicon wafers are temporarily supported on a base substrate such as glass via a temporary adhesive layer formed from a temporary adhesive resin composition. After this, processing steps such as wafer polishing and insulating film formation may be performed on the silicon wafer. It is required that the wafer exhibits minimal deformation and displacement even under the pressure of the processing steps, and that it exhibits excellent flatness after processing. Furthermore, in the above process, the two temporarily bonded substrates are separated by laser irradiation. It is also required that residue from the temporary adhesive layer be easily removed after laser delamination, but conventionally, achieving these has been difficult.

[0005] The present invention has been made in view of these circumstances, and aims to provide a method for manufacturing a semiconductor device in which, in the step of temporarily supporting a substrate to be subjected to a processing step via a temporary adhesive layer, a substrate with excellent flatness can be obtained after the processing step, and the temporary adhesive layer can be easily removed when the temporary support is released. The present invention also aims to provide a resin composition applicable to the above semiconductor manufacturing method, and a temporary adhesive resin composition.

[0006] Examples of typical embodiments of the present invention are shown below.

[0007] [1] A method for manufacturing a semiconductor device, comprising: a step of preparing a substrate A; a step of forming a temporary adhesive layer on one surface of the substrate A; a step of preparing a substrate B; and a bonding step of bonding the surface of the substrate A having the temporary adhesive layer and the substrate B; and a peeling step of irradiating a laser to peel the substrate A from the substrate B, wherein the temporary adhesive layer is a layer formed from a resin composition containing a polyamic acid ester.

[0008] [2] The method for manufacturing a semiconductor device according to [1], wherein the polyamic acid ester contains a repeating unit represented by the following formula (1).

[0009]

[0010] In formula (1), R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３ and R １１４ each independently represent a monovalent organic group.

[0011] [3] The method for manufacturing a semiconductor device according to [2], wherein at least one of R １１３ and R １１４ is a group represented by the following formula (III).

[0012]

[0013] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, R ２０１ represents an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group, and * represents a bonding site with an oxygen atom.

[0014] [4] The method for manufacturing a semiconductor device according to [2] or [3], wherein in the above formula (1), R １１１ is a group represented by the following formula (51).

[0015]

[0016] In formula (51), R５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of these is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (1).

[0017] [5] A method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the resin composition contains a surfactant. [6] A method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the viscosity of the resin composition is 500 mPa·s or more and less than 4000 mPa·s.

[0018] [7] A method for manufacturing a semiconductor device according to any one of [1] to [6], wherein the 5% mass loss temperature when the resin composition is cured is 450°C or higher. [8] A method for manufacturing a semiconductor device according to any one of [1] to [7], wherein the temporary adhesive layer formation step includes a step of spin-coating the resin composition onto the substrate A to form a resin film, and when the thickness of the resin film at a position 2 mm from the edge of the substrate A is X and the thickness of the resin film at a position 5 mm from the edge of the substrate A is Y, X / Y < 1.2.

[0019] [9] A method for manufacturing a semiconductor device according to any one of items [1] to [8], comprising an annealing step before the stripping step.

[10] A method for manufacturing a semiconductor device according to any one of items [1] to [9], comprising a cleaning step with a chemical solution after the stripping step.

[0020]

[11] A resin composition comprising a polyamic acid ester, used in the temporary adhesive layer formation step in the method for manufacturing a semiconductor device according to any one of [1] to

[10] .

[12] A temporary adhesive resin composition comprising a polyamic acid ester having repeating units represented by the following formula (1) and a solvent.

[0021]

[0022] In formula (1), R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３and R １１４ Each of these independently represents a monovalent organic group.

[0023]

[13] R １１３ and R １１４ The temporary adhesive resin composition according to

[12] , wherein at least one of the groups is represented by the following formula (III).

[0024]

[0025] In formula (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or polyalkylene oxy group, and * represents a bond site with an oxygen atom.

[0026]

[14] The temporary adhesive resin composition according to

[12] , comprising a surfactant.

[15] The temporary adhesive resin composition according to

[12] , wherein the content of polyamic acid ester is 80% by mass or more with respect to the total solid content of the resin composition.

[0027] According to the present invention, in a step of temporarily supporting a substrate to be processed via a temporary adhesive layer, it is possible to obtain a substrate with excellent flatness after the processing step, and to easily remove the temporary adhesive layer when releasing the temporary support, thereby providing a method for manufacturing semiconductor devices. Furthermore, according to the present invention, it is possible to provide a resin composition applicable to the above semiconductor manufacturing method, and a temporary adhesive resin composition.

[0028] This shows an example of the TBDB process in semiconductor manufacturing.

[0029] 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. 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.

[0030] (Method for Manufacturing Semiconductor Devices) The present invention provides a method for manufacturing semiconductor devices, comprising the steps of: preparing a substrate A; forming a temporary adhesive layer on one side of the substrate A; preparing a substrate B; joining the surface of the substrate A having the temporary adhesive layer to the substrate B; and peeling the substrate A from the substrate B by irradiating it with a laser, wherein the temporary adhesive layer is a layer formed from a resin composition containing a polyamic acid ester.

[0031] According to the semiconductor device manufacturing method of the present invention, in the step of temporarily supporting a substrate to be processed via a temporary adhesive layer, a substrate with excellent flatness can be obtained after the processing step, and the temporary adhesive layer can be easily removed when the temporary support is released. The mechanism by which the above effects are obtained is unknown, but it is presumed to be as follows.

[0032] First, there is a known embodiment in which the temporary adhesive layer is formed from a resin composition containing polyimide. When forming a temporary adhesive layer on a substrate other than the substrate to be processed (for example, glass), if spin coating is assumed, only soft resins tend to be able to be added to the spin coating solution in order to ensure solubility in the spin coating solution. In other words, when using polyimide to form the spin coating solution, it is difficult to incorporate a structure with so-called rigidity from the viewpoint of solubility, and it is difficult to obtain rigidity in the resulting temporary adhesive layer. After forming a temporary adhesive layer on a substrate other than the substrate to be processed using the spin coating solution, the surface of the substrate with the temporary adhesive layer is joined to the substrate to be processed, such as a silicon wafer. Subsequently, if the substrate to be processed is polished, for example, the temporary adhesive layer cannot be made into a rigid structure, so the substrate after polishing will have poor flatness. In contrast to this, the temporary adhesive layer in the semiconductor device manufacturing method of the present invention is formed from a resin composition containing polyamic acid ester. Because the resin composition contains a polyamic acid ester instead of the polyimide described above, as mentioned above, even when spin coating is assumed when forming the temporary adhesive layer, it becomes possible to incorporate a rigid structure into the polyamic acid ester. The resulting temporary adhesive layer also exhibits high rigidity. Therefore, similarly to the above, when a temporary adhesive layer is formed on a substrate separate from the substrate to be processed using a spin coating solution, and then the surface of the substrate with the temporary adhesive layer is joined to the substrate to be processed, such as a silicon wafer, and then the substrate to be processed is polished, for example, the temporary adhesive layer can be made into a rigid structure, and due to its rigidity, deformation is reduced even under pressure during polishing, resulting in a substrate with excellent flatness after polishing.

[0033] Furthermore, an embodiment is known in which the temporary adhesive layer is formed from a resin composition containing polyamic acid. When a temporary adhesive layer is formed from a resin composition containing polyamic acid, the polyamic acid is difficult to completely ring-close in the temporary adhesive layer (e.g., a cured film), so there is a high tendency for carboxylic acid to remain in the resulting temporary adhesive layer. When the substrate to be subjected to the processing step is temporarily supported via the temporary adhesive layer and the temporary support is finally released, even if cleaning with a chemical solution is performed, the remaining carboxylic acid will ultimately remain on the peeled substrate to be subjected to the processing step, resulting in poor removal of the temporary adhesive layer. In contrast, the temporary adhesive layer in the semiconductor device manufacturing method of the present invention is formed from a resin composition containing a polyamic acid ester. Because the resin composition contains a polyamic acid ester instead of the polyamic acid described above, as described above, the amount of remaining carboxylic acid can be kept low when forming a cured film as a temporary adhesive layer, for example. Therefore, it is believed that by performing a cleaning with a chemical solution when the temporary support is finally released after the substrate to be processed has been temporarily supported via a temporary adhesive layer, the removal of the temporary adhesive layer from the substrate to be processed will be excellent.

[0034] The following describes each step in the method for manufacturing the semiconductor device of the present invention.

[0035] <Step 1: Preparing Substrate A> Substrate A in Step 1 is not particularly limited, but examples include glass, quartz glass, alkali-free glass, etc. The shape of substrate A is not particularly limited and may be circular or rectangular. If the substrate A is circular, for example, the diameter is preferably 100 to 450 mm, and more preferably 200 to 450 mm. If the substrate A is rectangular, for example, the length of the shorter side is preferably 100 to 1000 mm, and more preferably 200 to 700 mm.

[0036] <Temporary adhesive layer formation step (step 2) for forming a temporary adhesive layer on one side of substrate A> As shown in Figure 1A, a temporary adhesive layer is formed on one side of substrate A. The temporary adhesive layer is a layer formed from a resin composition containing a polyamic acid ester. The polyamic acid ester in this invention is different from polyamic acid and includes a structure in which at least one of the carboxylic acids in the side chain of the polyamic acid is protected by an organic group. 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. Specifically, the polyamic acid ester has repeating units represented by the following formula (S).

[0037]

[0038] In formula (S), R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １３ and R １４ Each of these independently represents a hydrogen atom or a monovalent organic group. However, R １３ and R １４ At least one of them represents a monovalent organic group.

[0039] R １１１ , R １１５ These are R in equation (1) described below. １１１ , R １１５ The same applies to the preferred range. １３ and R １４ The monovalent organic group is R in formula (1) described below. １１３ and R １１４ This is similar to the monovalent organic group, and the preferred range is also the same.

[0040] Resin compositions containing polyamic acid esters will be described later.

[0041] In the context of temporary bonding layers, "temporary bonding" refers to a process where adhesion occurs initially, but can be removed through post-treatment. Specifically, it is not an irreversible bond that does not peel off once bonded.

[0042] <Step 3: Preparing Substrate B> Substrate B in Step 3 is not particularly limited, but examples include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. The shape of substrate B is not particularly limited and may be circular or rectangular. If the substrate B is circular, for example, the diameter is preferably 100 to 450 mm, and more preferably 200 to 450 mm. If the substrate B is rectangular, for example, the length of the shorter side is preferably 100 to 1000 mm, and more preferably 200 to 700 mm.

[0043] Substrate B is a substrate that will be used in the processing step.

[0044] <Bonding process (step 4) to join the surface of substrate A with the temporary adhesive layer to substrate B> As shown in Figures 1A and 1B, the surface of substrate A with the temporary adhesive layer to substrate B is joined. The bonding method is not particularly limited, but a wafer bonder, vacuum laminator, etc. can be used. The bonding temperature is not particularly limited, but it is preferably 150 to 250°C. The bonding pressure is not particularly limited, but it is preferably 0.1 to 1.0 MPa. The bonding time is not particularly limited, but it is preferably 1 to 60 minutes. In this way, as shown in Figure 1B, a bonded product (e.g., a wafer pair) is obtained in which the surface of substrate A with the temporary adhesive layer to substrate B is joined.

[0045] It is preferable that void formation is suppressed at the (temporary adhesive layer / substrate A interface, temporary adhesive layer / substrate B interface) of the resulting bond. Suppressing void formation improves the flatness of substrate B, and thus further improves the TTV suitability after wafer polishing. Void formation can be confirmed by visual inspection from the glass wafer surface.

[0046] The above-mentioned bonded object can be subjected to a processing step. Specifically, the side of the bonded object opposite to the side of the substrate B having the temporary adhesive layer can be subjected to the processing step. An example of a processing step is a polishing step.

[0047] <Polishing Process> The polishing process will be explained using Figures 2A and 2B. The side of substrate B opposite to the side with the temporary adhesive layer is ground by a grinding machine, and the surface of substrate B is ground as shown in Figure 2B to form substrate B1. The grinding machine is not particularly limited, but for example, a DISCO grinder can be used. The thickness of the resulting substrate B1 can be adjusted as appropriate depending on the application.

[0048] Another example of a process to be processed is the annealing process.

[0049] <Annealing Process> Substrates A and B, joined via a temporary adhesive layer, may be subjected to a heating process. This process is called the annealing process. As shown in Figure 2B, the objects to be processed may be substrates A and B1 joined via a temporary adhesive layer. In the annealing process, the surface of the side of substrate B opposite to the side with the temporary adhesive layer is oxidized, and an oxide film may be formed. The heating temperature in the annealing process is not particularly limited, but is preferably 200 to 400°C. Furthermore, the above process is preferably carried out under a nitrogen atmosphere. Furthermore, the heating time is not particularly limited, but is preferably 1 to 3 hours. The semiconductor manufacturing method of the present invention preferably includes an annealing process before the peeling process described later.

[0050] In substrates A and B joined via a temporary adhesive layer after the annealing process, it is preferable that the occurrence of voids at the (temporary adhesive layer / substrate A interface, temporary adhesive layer / substrate B interface) is suppressed. By suppressing the occurrence of voids, the flatness of substrate B is improved, and the effect of improving TTV suitability after wafer polishing is further obtained. The occurrence of voids can be confirmed by visual inspection from the glass wafer surface.

[0051] The semiconductor manufacturing method of the present invention includes a peeling step of peeling the substrate A from the substrate B by irradiating it with a laser.

[0052] <Peeling process to peel substrate A from substrate B (Step 4)> The peeling process will be explained using Figures 2C and 2D. As an example, the substrate B will be described using the configuration in which it is subjected to the polishing process described above to become substrate B1. In the substrate A and substrate B1 joined via a temporary adhesive layer as shown in Figure 2C, a laser is irradiated using the laser irradiation device 6 from the side of substrate A opposite to the side with the temporary adhesive layer. Laser is an abbreviation for "Light Amplification of Stimulated Emission of Radiation," and is monochromatic, has excellent directionality and straightness, and has properties different from electromagnetic waves. The laser is not particularly limited, but is not limited as long as it is light with a wavelength that can sublimate and decompose the temporary adhesive layer. For example, an excimer laser can be used. The laser irradiation device is not particularly limited. Also, the irradiation time is not particularly limited and is adjusted as appropriate considering the object being used. As described above, when a laser is applied, substrate A and substrate B1 are separated. This is because the adhesion of the temporary adhesive layer decreases due to the laser irradiation. "Separation" means peeling off and separating. For example, as shown in Figure 2D, substrate A and substrate B1 are separated.

[0053] The semiconductor manufacturing method of the present invention preferably includes a cleaning step with a chemical solution after the stripping step described above.

[0054] <Cleaning process with chemical solution> The chemical solution used in the cleaning process is not particularly limited, but for example, a mixture of 70% by mass of monoethanolamine and 30% by mass of DMSO (dimethyl sulfoxide) is used. Specifically, it is preferable to immerse the peeled substrate B (substrate B1 as an example) in the above mixture to remove the temporary adhesive layer remaining on the substrate B. The temperature of the chemical solution is not particularly limited, but for example, it can be 80 to 120°C. The immersion time is not particularly limited, but for example, it can be 0.5 to 3 hours.

[0055] The following describes a resin composition containing a polyamic acid ester (hereinafter also referred to as "the resin composition of the present invention"). [Resin composition] A polyamic acid ester is a so-called polyimide precursor, and 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 polyamic acid ester preferably has polymerizable groups, and more preferably contains radical polymerizable groups. When the polyamic acid ester has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, the polyamic acid ester may have polarity conversion groups such as acid-degradable groups.

[0056] (Polyamic acid ester) The polyamic acid ester in the present invention preferably has repeating units represented by the following formula (1).

[0057]

[0058] In formula (1), 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 monovalent organic group.

[0059] R in equation (1) 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.

[0060] Also, R １１１ It is preferable that is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of rigidity and availability, it is more preferable that it is a divalent organic group represented by formula (61). In addition, as a preferred embodiment, R １１１Preferably, the group is a divalent organic group represented by the following formula (51). The above structure allows for the introduction of a rigid unit into the polyamic acid ester, which increases the Young's modulus of the resulting cured film. This is preferable because, for example, after bonding substrate A and substrate B, to which a temporary adhesive layer is provided, the surface of substrate B can be stably polished.

[0061]

[0062] In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and 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 (1). 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).

[0063]

[0064] In formula (61), R ５８ and R ５９ Each 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 (1). 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.

[0065] R in equation (1) 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.

[0066]

[0067] 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 - More preferably, 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 -.

[0068] 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.

[0069] R in equation (1) １１５ It is preferable that it is represented by the following formula (a) or (b).

[0070]

[0071] In formula (a) or formula (b), * represents the bonding site with the carbonyl group in formula (1).

[0072] In equation (1), R １１１ and R １１５ It is also possible that at least one of them has an OH group. More specifically, R １１１ Examples include residues of bisaminophenol derivatives.

[0073] R in equation (1) １１３ and R １１４Each of these independently represents 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 polymerizable groups. １１３ and R １１４ It is also preferable that at least one of the groups 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 ethylenically unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups in the polyimide precursor, groups having ethylenically unsaturated bonds are preferred. 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, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred. In one preferred embodiment, R １１３ and R １１４ Preferably, at least one of the groups is represented by the following formula (III).

[0074]

[0075] In formula (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or polyalkylene oxy group, and * represents a bond site with an oxygen atom.

[0076] 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), R ２０１represents an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. Examples of preferred R ２０１ include alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, etc., a 1,2-butanediyl group, a 1,3-butanediyl group, -CH ２ CH(OH)CH ２ -, and polyalkyleneoxy groups, alkylene groups such as an ethylene group, a propylene group, etc., -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 alternating patterns. 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, 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.

[0077] In equation (1), R １１３and R １１４ At least one of these 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 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.

[0078] It is also preferable that the polyamic acid ester has a fluorine atom in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0079] Furthermore, to improve adhesion to the substrate, the polyamic acid ester 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.

[0080] Polyamic acid esters may contain one type of repeating unit represented by formula (1), or two or more types. They may also contain structural isomers of the repeating unit represented by formula (1). In addition to the repeating unit of formula (1), polyamic acid esters may also contain other types of repeating units.

[0081] One embodiment of the polyamic acid ester in the present invention is one in which the content of repeating units represented by formula (1) 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 above upper limit of the total content is not particularly limited, and all repeating units in the polyamic acid ester except for the terminals may be repeating units represented by formula (1).

[0082] The weight-average molecular weight (Mw) of the polyamic acid ester 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 polyamic acid ester 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 polyamic acid ester 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 polyamic acid ester, 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 the resin composition contains multiple types of polyamic acid esters, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamic acid esters are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyamic acid esters are treated as a single resin are, respectively, within the above ranges.

[0083] [Content] The content of polyamic acid ester in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of polyamic acid ester in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% 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 polyamic acid ester, or it may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0084] The resin composition of the present invention may also preferably contain at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of polyamic acid esters and other resins described later, or it may contain two or more types of polyamic acid esters, but it is preferable to contain two or more types of polyamic acid esters. When the resin composition of the present invention contains two or more types of polyamic acid esters, for example, the polyamic acid ester may have a structure derived from a dianhydride (R in formula (1) above). １１５ Preferably, the polyamic acid esters contain two or more different types of polyamic acid esters.

[0085] <Other Resins> The resin composition of the present invention may contain the polyamic acid ester described above and other resins different from the polyamic acid ester (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, etc. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a polymerizable compound with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10) may be used. －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0086] 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.

[0087] <Surfactants> The resin composition of the present invention preferably contains a surfactant. In the temporary adhesive layer formation step, in which a temporary adhesive layer is formed on one side of a substrate A, for example, when the temporary adhesive layer is formed from the resin composition of the present invention by a spin coating method, the resin composition spreads from the center of the substrate A to the edges, so the amount of resin composition applied tends to be larger at the edges. In such a state, voids may be generated when bonding with substrate B in the bonding step. The resin composition of the present invention is preferable because it contains a surfactant, which allows the resin composition to be applied uniformly to the substrate A, thereby suppressing the generation of voids during the above bonding. Various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used as the surfactant. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0088] By incorporating a surfactant into the resin composition, the liquid properties (especially fluidity) of the composition are improved, leading to improved uniformity of coating thickness and reduced liquid consumption, as well as increased conformability of the composition to uneven surfaces. Specifically, when forming a film using a coating solution containing a surfactant, the interfacial tension between the surface to be coated and the coating solution decreases, improving wettability to the surface and enhancing coatability. As a result, air bubbles are less likely to be incorporated into uneven areas, and a more uniform film with less thickness variation can be formed more effectively.

[0089] 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.

[0090] 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.

[0091] <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.

[0092] [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.

[0093] 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.

[0094] 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.

[0095] 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 with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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).

[0100] 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.

[0101] 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.

[0102] 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 polymerizability. The above acid value is measured in accordance with the description in JIS K 0070:1992. As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is 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.

[0103] 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, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-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.

[0104] 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.

[0105] 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.

[0106] [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 their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to a photoacid generator or photobase generator described later, and are preferably compounds having multiple groups in their 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 a base. 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.

[0107] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The other crosslinking agents may be present as one type or as two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0108] A preferred embodiment of the resin composition of the present invention is one which contains a first polymerizable compound and a second polymerizable compound different from the first polymerizable compound. The first polymerizable compound and the second polymerizable compound are examples of the polymerizable compounds mentioned above. It is preferable that the first polymerizable compound is a polyfunctional (meth)acrylate with three or more functions. It is preferable that the second polymerizable compound is a bifunctional (meth)acrylate. The ratio of the first polymerizable compound to the second polymerizable compound is not particularly limited, but it is preferable that the mass ratio of the first polymerizable compound to the second polymerizable compound is 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1. When the resin composition of the present invention contains polymerizable compounds, polymerization can be carried out by heating. The heating temperature (maximum heating temperature) is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0109] <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 precursor of a cyclized resin, 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, amineimide 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.

[0110] Examples of base-generating agents include, but are not limited to, the following compounds.

[0111]

[0112] 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.

[0113] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0114] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0115]

[0116] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0117]

[0118] 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.

[0119] <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.

[0120] 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, 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.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (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.).

[0121] 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.

[0122] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0123] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0124] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0125] 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.

[0126] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0127] 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.

[0128] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0129] 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, 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 resin composition of the present invention preferably contains a solvent, and it is preferable that the solvent contains at least one selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone. As the solvent, a combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0130] 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.

[0131] <Metal Adhesion Enhancers> From the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc., the resin composition preferably contains a metal adhesion enhancer. 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.

[0132] [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.).

[0133]

[0134] Examples of other silane coupling agents include 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-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more. Also, as the silane coupling agent, an oligomer type compound having a plurality of alkoxysilyl groups can be used. Examples of such an oligomer type compound include a compound containing a repeating unit represented by the following formula (S-1).

[0135]

[0136] In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. R 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.).

[0137] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0138] 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.

[0139] 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.

[0140] <Migration Inhibitor> The resin composition 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.

[0141] 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.

[0142] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0143] 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.

[0144] If the resin composition 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.

[0145] 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.

[0146] <Polymerization Inhibitors> The resin composition 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 ring compounds, and metal compounds.

[0147] 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.

[0148] If the resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0149] 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.

[0150] <Other Additives> The resin composition 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 can be 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 the contents of these 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.

[0151] <Characteristics of the Resin Composition> The viscosity of the resin composition is preferably 400 mPa·s or more and 4500 mPa·s or less, and more preferably 500 mPa·s or more and less than 4000 mPa·s. Within the above range, it is easy to obtain a coating film with high uniformity. The viscosity of the resin composition is expressed as the liquid viscosity at 25°C measured with an E-type viscometer TR-100 (manufactured by Toki Sangyo Co., Ltd.).

[0152] <Restrictions on the substances contained in the resin composition> The water content of the resin composition is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the 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.

[0153] From the viewpoint of insulating properties, the metal content of the resin composition 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.

[0154] Furthermore, methods for reducing metal impurities unintentionally included in resin compositions include selecting raw materials with low metal content as components of the resin composition, filtering the raw materials of the resin composition, and performing distillation under conditions that suppress contamination as much as possible by lining the apparatus with polytetrafluoroethylene or the like.

[0155] The resin composition preferably contains less than 500 ppm by mass of halogen atoms, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of preventing wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chloride ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0156] Conventional containers can be used as containers for the resin composition. To suppress the incorporation of impurities into the raw materials and resin composition, 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.

[0157] <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.

[0158] 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. Paragraph 0287 of International Publication No. 2023 / 190064 is incorporated herein by reference as part of this specification.

[0159] In a preferred embodiment, the 5% mass loss temperature when the resin composition of the present invention is cured is preferably 330°C or higher, more preferably 400°C or higher, and even more preferably 450°C or higher. The above 5% mass loss temperature can be determined as follows: The cured film obtained by curing the resin composition at 200°C for 2 hours is heated at 10°C / min using a TGA 5500 (manufactured by TA Instruments) and the temperature at which the mass loss reaches 5% by mass is defined as the 5% mass loss temperature (Td5%). A higher 5% mass loss temperature makes it less likely for the resin composition to undergo mass loss in the cured film. In other words, it is preferable because it can suppress the generation of outgassing associated with the heating of the cured product, and therefore, in the semiconductor manufacturing method of the present invention, it is possible to suppress the generation of voids when joining substrate A, a temporary adhesive layer, and substrate B, and the generation of voids when performing the above annealing process.

[0160] <Temporary Adhesive Layer Formation Process> In step 2 above, a temporary adhesive layer is formed on one side of substrate A. The temporary adhesive layer is a layer formed from a resin composition containing a polyamic acid ester.

[0161] (Film Formation Process) The resin composition of the present invention can be used in the process of forming a layer by applying it to one side of a substrate A to form a film. Preferably, the process of forming a temporary adhesive layer of the present invention includes a film formation process by applying the resin composition to one side of a substrate A to form a film.

[0162] Specific methods for applying the resin composition to one side of substrate A 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 resin composition and the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected 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 spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. In one preferred embodiment, it is preferable to form a film on one side of substrate A by spin coating.

[0163] Alternatively, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred to one side of the substrate A. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. Furthermore, a step to remove excess film at the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which one side of the substrate A is coated with various solvents to improve its wettability before applying the resin composition to one side of the substrate A, and then the resin composition is applied.

[0164] (Drying step) After the film formation step (layer formation step), the film may be subjected to a drying step to remove the solvent from the formed film (layer). That is, the temporary adhesive layer formation step in the semiconductor manufacturing method of the present invention may include a drying step to dry the film formed in the film formation step. The drying step is preferably performed after the film formation step and before the exposure step. The drying temperature of the film 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.

[0165] (Heating step) The above film, or the film subjected to the drying step, may be subjected to a heating step. That is, the step of forming a temporary adhesive layer in the semiconductor manufacturing method of the present invention may include a heating step of heating the above film, or the film subjected to the drying step. In the heating step, the polyamic acid ester is cyclized to become a resin such as polyimide. In addition, crosslinking of unreacted crosslinkable groups (polymerizable groups) in the polyamic acid ester or other crosslinking agents also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C. Paragraphs 0326 to 0332 of International Publication No. 2023 / 190064 are incorporated herein by reference as part of this specification. After the above heating step, in step 2, a temporary adhesive layer is formed on one side of the substrate A. The temporary adhesive layer is a cured product of the resin composition of the present invention.

[0166] In a preferred embodiment, the temporary adhesive layer formation step includes a step of spin-coating the resin composition onto the substrate A to form a resin film, wherein, when the thickness of the resin film at a position 2 mm from the edge of the substrate A is X and the thickness of the resin film at a position 5 mm from the edge of the substrate A is Y, it is preferable that X / Y < 1.2.

[0167] X and Y are measured as follows: Using an optical interference film thickness analyzer VM-2500 (manufactured by SCREEN Corporation), the resin film thickness is measured at 10 points 2 mm from the edge of substrate A, and the average value is taken as X. The resin film thickness is measured at 10 points 5 mm from the edge of substrate A, and the average value is taken as Y.

[0168] X / Y is preferably less than 1.1. The lower limit of X / Y is not particularly limited, but for example, it is 1.

[0169] The present invention also relates to the following resin composition: a resin composition comprising a polyamic acid ester, used in the temporary adhesive layer formation step in the semiconductor device manufacturing method of the present invention. The polyamic acid ester is the same as the polyamic acid ester in the temporary adhesive layer formation step in the semiconductor device manufacturing method of the present invention, and the preferred embodiment is also the same. Furthermore, the above resin composition is the same as the resin composition in the semiconductor device manufacturing method of the present invention, and the preferred embodiment is also the same.

[0170] Furthermore, the present invention also relates to the following temporary adhesive resin composition: A temporary adhesive resin composition comprising a polyamic acid ester having repeating units represented by the following formula (1) and a solvent.

[0171]

[0172] In formula (1), 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 monovalent organic group.

[0173] Each group in formula (1) is the same as each group in the repeating unit represented by formula (1) in the semiconductor manufacturing method of the present invention described above, and the preferred range is also the same. Furthermore, the preferred range of the polyamic acid ester in the temporary adhesive resin composition described above is the same as the preferred range of the polyamic acid ester in the semiconductor manufacturing method of the present invention. The solvent is the same as the solvent that may be included in the resin composition in the semiconductor manufacturing method of the present invention described above, and the preferred range is also the same. The temporary adhesive resin composition may contain each component that may be included in the resin composition in the semiconductor manufacturing method of the present invention described above, and the preferred range is also the same.

[0174] R １１３ and R １１４ Preferably, at least one of the groups is represented by the following formula (III).

[0175]

[0176] In formula (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or polyalkylene oxy group, and * represents a bond site with an oxygen atom.

[0177] Each group in formula (III) is the same as in formula (III) in the semiconductor manufacturing method of the present invention described above, and the preferred range is also the same.

[0178] The temporary bonding resin composition preferably contains a surfactant. The surfactant is the same as the surfactant that may be included in the resin composition in the semiconductor manufacturing method of the present invention described above, and the preferred range is also the same. Furthermore, it is preferable that the polyamic acid ester content of the above resin composition is 80% by mass or more with respect to the total solid content.

[0179] 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.

[0180] <Synthesis of Polyamic Acid Esters> [Synthesis Example 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 are mixed and stirred at 60°C for 18 hours to produce a diester of 4',4-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture is then cooled and 16.12 g (135.5 mmol) of SOCl is added. ２ The solution is added over 2 hours. Then, a solution of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 2 hours while adjusting the temperature to a range of -5 to 0°C. The reaction mixture is allowed to react at 0°C for 1 hour, then 70 g of ethanol is added and the mixture is stirred at room temperature for 1 hour. Next, the polyamic acid ester is precipitated in 5 liters of water, and the water-polyamic acid ester mixture is stirred at a speed of 5000 rpm (revolution per minute) for 15 minutes. The polyamic acid ester is filtered out, stirred again in 4 liters of water for 30 minutes, and filtered again. The resulting polyamic acid ester is then dried under reduced pressure for 2 days. The weight-average molecular weight of this resin (P-1) is 20,000. Resin (P-1) is a resin having repeating units represented by the following formula (P-1). The structure of the repeating unit is １ It is determined from the H-NMR spectrum.

[0181]

[0182] [Synthesis Example 2: Synthesis of Resin (P-2)] 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 (HEMA), 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 diglyceride (diethylene glycol dimethyl ether) are mixed. The mixture is stirred at 60°C for 4 hours to produce a mixture of 2-hydroxyethyl methacrylate and 2-isobutoxyethanol diesters of 4,4'-oxydiphthalic anhydride and 3,3',4,4'-biphenyltetracarboxylic anhydride. 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. ２ After 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'-diamino-2,2'-dimethylbiphenyl dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -5°C 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 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 to precipitate the polyamic acid ester. The polyamic acid ester is obtained by filtration, and the obtained polyamic acid ester is dried under reduced pressure at 45°C for 1 day to obtain the crude polyamic acid ester (P-2). 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 speed of 400 rpm to precipitate the polyamic acid ester. The polyamic acid ester is obtained by filtration, and the resulting polyamic acid ester is dried under reduced pressure at 45°C for 1 day to obtain polyamic acid ester (P-2). The weight-average molecular weight of this polyamic acid ester (P-2) is 23,000. １¹H-NMR confirms that the resulting polyamic acid ester (P-2) contains repeating units represented by the following formula (P-2). In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit. １ ¹H-NMR confirmed that the imidization rate of the polyamic acid ester was 0% and the HEMA introduction rate was 70 mol%.

[0183]

[0184] [Synthesis Example 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, 17.2 g (131.8 mmol) of 2-hydroxyethyl methacrylate (HEMA), 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 diesters of 2-hydroxyethyl methacrylate of 4,4'-oxydiphthalic anhydride and 3,3',4,4'-biphenyltetracarboxylic anhydride. The reaction mixture is then cooled to -10°C, and while maintaining the temperature at -10±4°C, 16.14 g (134.1 mmol) of SOCl 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'-diamino-2,2'-dimethylbiphenyl dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -5°C 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 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 to precipitate the polyamic acid ester. The polyamic acid ester is obtained by filtration, and the obtained polyamic acid ester is dried under reduced pressure at 45°C for 1 day to obtain the crude polyamic acid ester (P-3). 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 speed of 400 rpm to precipitate the polyamic acid ester. The polyamic acid ester is obtained by filtration, and the resulting polyamic acid ester is dried under reduced pressure at 45°C for 1 day to obtain polyamic acid ester (P-3). The weight-average molecular weight of this polyamic acid ester (P-3) is 21,000. １ ¹H-NMR confirms that the resulting polyamic acid ester (P-3) contains repeating units represented by the following formula (P-3). In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit. １ ¹H-NMR confirmed that the imidization rate of the polyamic acid ester was 0% and the HEMA introduction rate was 100 mol%.

[0185]

[0186] [Synthesis Example 4: Synthesis of Resin (P-4)] 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 (HEMA), 2.4 g (39.5 mmol) of 1-propanol, 0.05 g of hydroquinone, 22.7 g of pyridine (287 mmol), and 75 g of diglyceride (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 1-propanol. 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. ２ After 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'-diamino-2,2'-dimethylbiphenyl dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -5°C 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 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 to precipitate the polyamic acid ester. The polyamic acid ester is obtained by filtration, and the obtained polyamic acid ester is dried under reduced pressure at 45°C for 1 day to obtain the crude polyamic acid ester (P-4). 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 speed of 400 rpm to precipitate the polyamic acid ester. The polyamic acid ester is obtained by filtration, and the resulting polyamic acid ester is dried under reduced pressure at 45°C for 1 day to obtain polyamic acid ester (P-4). The weight-average molecular weight of this polyamic acid ester (P-4) is 22,500. １¹H-NMR confirms that the resulting polyamic acid ester (P-4) contains repeating units represented by the following formula (P-4). In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit. １ ¹H-NMR confirmed that the imidization rate of the polyamic acid ester was 0% and the HEMA introduction rate was 70 mol%.

[0187]

[0188] [Synthesis Example 5: Synthesis of Resin (P-5)] 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic acid anhydride are placed in a reaction vessel, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 mL of γ-butyrolactone are added. While stirring at room temperature, 7.91 g of pyridine is added to obtain the reaction mixture. After the exothermic reaction is complete, the mixture is allowed to cool to room temperature and left for a further 16 hours. Next, under ice cooling, a solution of 206 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 30 mL of γ-butyrolactone is added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 mL of γ-butyrolactone is added over 60 minutes with stirring. After stirring at room temperature for 2 hours, 3 mL of ethyl alcohol is added and the mixture is stirred for 1 hour. Then, 100 mL of γ-butyrolactone is added. The precipitate formed in the reaction mixture is removed by filtration to obtain the reaction solution. The obtained reaction solution is added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polyamic acid ester. The crude material is filtered and then vacuum-dried to obtain powdered polyamic acid ester (P-5). The weight-average molecular weight of this polyamic acid ester (P-5) is 27,900. １ ¹H-NMR confirms that the resulting polyamic acid ester (P-5) contains repeating units represented by the following formula (P-5). In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0189]

[0190] [Synthesis Example 6: Synthesis of Resin (P-6)] Resin (P-6) is obtained in the same manner as in Synthesis Example 1 of International Publication No. 2023 / 171014. The weight-average molecular weight of this resin (P-6) is 22,000. １ H-NMR confirms that the resulting resin (P-6) contains repeating units represented by the following formula (P-6). In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0191]

[0192] [Synthesis Example C1: Synthesis of Resin (CP-1) (for Comparative Example)] Resin (CP-1) is obtained in the same manner as in Example 1 of International Publication No. 2024 / 058061. The weight-average molecular weight of this resin (CP-1) is 30,000. １ H-NMR confirms that the resulting resin (CP-1) contains repeating units represented by the following formula (CP-1).

[0193]

[0194] [Synthesis Example C2: Synthesis of Resin (CP-2) (for Comparative Example)] Resin (CP-2) is obtained in the same manner as in Example 1 of Japanese Patent Publication No. 2017-530206. The weight-average molecular weight of this resin (CP-2) is 25,000. １ H-NMR confirms that the resulting resin (CP-2) contains repeating units represented by the following formula (CP-2).

[0195]

[0196] [Method for measuring weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin are determined using an HLC-8420GPC (manufactured by Tosoh Corporation) with two TSKguardcolumn SuperAW-H and two TSK SuperAWM-H columns (both manufactured by Tosoh Corporation) connected in series. An NMP solution is used as the eluent, and the values ​​are detected as polystyrene equivalent values ​​using a UV (ultraviolet) wavelength detector at 275 nm.

[0197] The weight-average molecular weight (Mw) of each of the above resins is shown in the table below.

[0198] <Examples and Comparative Examples> In each example, the components listed in the table below are mixed to obtain each resin composition. Similarly, in each comparative example, the components listed in the table below are mixed to obtain each comparative composition. Specifically, the content of each component listed in the table is the amount (parts by mass) indicated in the "parts by mass" column of each column in the table. The amount of solvent used is such that the solid content concentration of the composition is the "solid content concentration (mass%)" in the table, and the solvent is mixed at the mixing ratio (mass ratio) indicated in the "ratio" column of each solvent. The obtained resin compositions and comparative compositions are subjected to pressure filtration using a polytetrafluoroethylene filter with a pore size of 0.8 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[0199]

[0200]

[0201]

[0202]

[0203] [Resins] ・P-1 to P-6: The above resins (P-1) to (P-6) ・CP-1, CP-2: The above resins (CP-1) and (CP-2) P-1 to P-6 are polyamic acid esters. CP-1 and CP-2 are resins that do not fall under the category of polyamic acid esters.

[0204] [Polymerizable Compounds] • B-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • B-2: NK Ester TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • B-3: A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • B-4: NK Ester A-9300S (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • B-5: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0205] [Polymerization Inhibitors] ・A-1: Compound with the following structure ・A-2: N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] ・A-3: Dibutylhydroxytoluene (BHT) ・A-4: Semihindered phenol ・A-5: 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)

[0206]

[0207] [Silane Coupling Agents] ・D-1, D-4 to D-7: Compounds with the following structure. In the following structural formulas, Me represents a methyl group and Et represents an ethyl group. D-7 is X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd.). ・D-2: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・D-3: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・D-8: 50% methanol solution of 3-ureidopropyltriethoxysilane

[0208]

[0209] [Surfactants] ・F-1: BYK-333 (manufactured by BYK) ・F-2: BYK-UV3510 (manufactured by BYK) ・F-3: BYK-3760 (manufactured by BYK) ・F-4: DOWSIL 67 Additive (manufactured by Dow) ・F-5: DOWSIL 74 Additive (manufactured by Dow) ・F-6: DOWSIL SH 8400 FLUID (manufactured by Dow)

[0210] [Thermal base generating agents] ・G-1 to G-4: Compounds represented by the following formulas (G-1) to (G-4)

[0211]

[0212] [Solvents] H-1: γ-butyrolactone, H-2: dimethyl sulfoxide, H-3: ethyl lactate, H-4: N-methyl-2-pyrrolidone, H-5: γ-valerolactone, H-6: toluene

[0213] [5% Mass Loss Temperature] The 5% mass loss temperature of the resin compositions according to each example and comparative example when cured is determined as follows. The cured film obtained by curing each resin composition at 200°C for 2 hours is heated at 10°C / min using a TGA 5500 (manufactured by TA Instruments) until the mass loss reaches 5% by mass. This temperature is defined as the 5% mass loss temperature (Td5%). The 5% mass loss temperature is indicated as "Td5%" in the table.

[0214] [Viscosity of Resin Compositions] The viscosity of the resin compositions for each example and comparative example is determined as follows. The viscosity of the resin composition represents the liquid viscosity at 25°C, measured with an E-type viscometer TR-100 (manufactured by Toki Sangyo Co., Ltd.).

[0215] <Example 1> (TBDB process) A glass wafer (substrate A) with a diameter of 300 mm is prepared, and the resin composition of Example 1 is applied to one side of substrate A by spin coating to a thickness of 7.5 μm. After application, it is dried at 100°C for 5 minutes to form a temporary adhesive layer. It is cured at 200°C for 2 hours in a nitrogen atmosphere. A substrate to be polished (specifically, a silicon wafer with a thickness of 775 μm (also called "substrate B")) is prepared. The side of substrate A with the temporary adhesive layer and substrate B are bonded together using a wafer bonder at a temperature of 260°C, a pressure of 0.3 MPa, and a time of 10 minutes to form a bonded product. The side of the bonded product opposite to the side of substrate B with the temporary adhesive layer is cut using a DISCO grinder until the thickness of substrate B is 30 μm. The bonded product after cutting is heated at 350°C for 1 hour in a nitrogen atmosphere. A 308 nm laser peeling machine manufactured by Suss is used with a laser dose of 250 mJ / cm². ２ The light is irradiated from the glass surface to separate the glass wafer (substrate A) from the substrate (substrate B).

[0216] <Examples 2-41, Comparative Examples 1 and 2> (TBDB process) The TBDB process is carried out in the same manner as in Example 1, except that the resin composition of Examples 2-41 and Comparative Examples 1 and 2 are used instead of the resin composition of Example 1, and the laser dose is changed to the value shown in the table. In Example 9, the above-mentioned process of heating the joined material after cutting at 350°C for 1 hour in a nitrogen atmosphere (so-called annealing process) is not performed.

[0217] In each example and comparative example, when the thickness of the resin film (temporary adhesive layer) at a position 2 mm from the edge of substrate A is X, and the thickness of the resin film (temporary adhesive layer) at a position 5 mm from the edge of substrate A is Y, the value of X / Y is calculated.

[0218] X and Y are measured as follows: Using an optical interference film thickness analyzer VM-2500 (manufactured by SCREEN Corporation), the resin film thickness is measured at 10 points 2 mm from the edge of substrate A, and the average value is taken as X. The resin film thickness is measured at 10 points 5 mm from the edge of substrate A, and the average value is taken as Y.

[0219] <Evaluation> The evaluation will be based on flatness and the amount of residue remaining after residue removal, as follows.

[0220] [Flatness] In the TBDB process described above in each example and comparative example, the substrate B peeled off using a Suss 308 nm laser peeler is immersed in a chemical solution (70% by mass monoethanolamine / 30% by mass DMSO) at 105°C for 2 hours. After immersion, the substrate B is washed with water and dried in an oven at 105°C for 30 minutes, and the TTV of the substrate B is evaluated using a Kobelco Research Institute (product code: LTV-3001). TTV represents the difference between the maximum and minimum thickness (distance from the back surface reference plane) when the substrate B (wafer) is adsorbed and fixed. (Evaluation criteria) S: 0.5 μm or less A: Greater than 0.5 μm and 1 μm or less B: Greater than 1 μm and 2 μm or less C: Greater than 2 μm

[0221] [Residue after residue removal] In the TBDB process described above in each example and comparative example, substrate B, which was peeled off using a Suss 308 nm laser peeler, is immersed in a chemical solution (70% by mass of monoethanolamine / 30% by mass of DMSO) at 105°C. The following evaluation criteria are used: (Evaluation criteria) A: No residue is visible after 1 hour of chemical treatment. B: No residue is visible after 2 hours of chemical treatment. C: Residue is still visible after 2 hours of chemical treatment.

[0222] Furthermore, voids after bonding and voids after the annealing process are also evaluated as follows: [Voids after bonding] In the TBDB process described above in each example and comparative example, the presence or absence of voids at the interface between the temporary adhesive layer and the substrate is visually confirmed for the bonded product after bonding. (Evaluation criteria) A: No voids at the interface between the temporary adhesive layer and the substrate B: Voids are present at the interface between the temporary adhesive layer and the substrate

[0223] [Voids after annealing] In the TBDB process described above in each example and comparative example, the presence or absence of voids at the interface between the temporary adhesive layer and the substrate is visually confirmed in the bonded product after the annealing process. (Evaluation criteria) A: No voids at the interface between the temporary adhesive layer and the substrate B: Voids are present at the interface between the temporary adhesive layer and the substrate

[0224] According to the present invention, in the step of temporarily supporting a substrate to be processed via a temporary adhesive layer, a substrate with excellent flatness can be obtained after the processing step, and the temporary adhesive layer can be easily removed when the temporary support is released.

[0225] According to the present invention, in a step of temporarily supporting a substrate to be processed via a temporary adhesive layer, it is possible to obtain a substrate with excellent flatness after the processing step, and to easily remove the temporary adhesive layer when releasing the temporary support, thereby providing a method for manufacturing semiconductor devices. Furthermore, according to the present invention, it is possible to provide a resin composition applicable to the above semiconductor manufacturing method, and a temporary adhesive resin composition.

[0226] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2025-007134 filed on 17 January 2025, the contents of which are incorporated herein by reference.

[0227] 1. Substrate A 2. Temporary adhesive layer 3. Substrate B 4. Polishing machine 5. Substrate B1 6. Laser irradiation device

Claims

1. A method for manufacturing a semiconductor device, comprising the steps of: preparing a substrate A; forming a temporary adhesive layer on one side of the substrate A; preparing a substrate B; joining the surface of the substrate A having the temporary adhesive layer to the substrate B; and peeling the substrate A from the substrate B by irradiating it with a laser, wherein the temporary adhesive layer is a layer formed from a resin composition containing a polyamic acid ester.

2. The method for manufacturing a semiconductor device according to claim 1, wherein the polyamic acid ester comprises a repeating unit represented by the following formula (1). In formula (1), 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 monovalent organic group.

3. R １１３ and R １１４ The method for manufacturing a semiconductor device according to claim 2, wherein at least one of them is a group represented by the following formula (III). In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and R ２０１ represents an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group, and * represents a bonding site with an oxygen atom.

4. In formula (1) above, R １１１ A method for manufacturing a semiconductor device according to claim 2, wherein the group is represented by the following 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, and R ５０ ~R ５７ At least one of these is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (1).

5. A method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein the resin composition contains a surfactant.

6. A method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein the viscosity of the resin composition is 500 mPa·s or more and less than 4000 mPa·s.

7. A method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein the temperature at which the resin composition is cured is 450°C or higher.

8. The method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein the temporary adhesive layer formation step includes a step of spin-coating the resin composition onto the substrate A to form a resin film, and when the thickness of the resin film at a position 2 mm from the edge of the substrate A is X and the thickness of the resin film at a position 5 mm from the edge of the substrate A is Y, X / Y < 1.

2.

9. A method for manufacturing a semiconductor device according to any one of claims 1 to 4, comprising an annealing step prior to the stripping step.

10. A method for manufacturing a semiconductor device according to any one of claims 1 to 4, comprising a cleaning step with a chemical solution after the stripping step.

11. A resin composition comprising a polyamic acid ester, used in the temporary adhesive layer formation step in the method for manufacturing a semiconductor device according to any one of claims 1 to 4.

12. A temporary adhesive resin composition comprising a polyamic acid ester having repeating units represented by the following formula (1) and a solvent. In formula (1), 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 monovalent organic group.

13. R １１３ and R １１４ The temporary adhesive resin composition according to claim 12, wherein at least one of the groups is represented by the following formula (III). In formula (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or polyalkylene oxy group, and * represents a bond site with an oxygen atom.

14. The temporary adhesive resin composition according to claim 12, comprising a surfactant.

15. The temporary adhesive resin composition according to claim 12, wherein the content of polyamic acid ester is 80% by mass or more with respect to the total solid content of the resin composition.

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