Photosensitive resin composition, method for producing electronic device, electronic device, and light device

Abstract

To provide a photosensitive resin composition that exhibits a large focus margin while offering moderate stretchability.SOLUTION: The present invention provides: a photosensitive resin composition which contains (A) a polyimide resin, (B) a multifunctional (meth)acrylate compound, (C) a sensitizing agent and (D) a polymerization inhibitor, wherein the polyimide resin (A) comprises a structure represented by general formula (a) (in the general formula (a), X represents a divalent organic group, and Y represents a tetravalent organic group); an electronic device which includes an insulating layer that is formed of this photosensitive resin composition; and a light device which includes an insulating layer that is formed of this photosensitive resin composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing an electronic device, an electronic device, and an optical device. [Background technology]

[0002] In the electrical and electronics fields, photosensitive resin compositions containing polyamide resins and / or polyimide resins are sometimes used to form cured films such as insulating layers, etc. For this reason, photosensitive resin compositions containing polyamide resins and / or polyimide resins have been studied.

[0003] As an example, Patent Document 1 describes a photosensitive composition that includes at least one fully imidized polyimide polymer having a weight average molecular weight in the range of about 20,000 daltons to about 70,000 daltons; at least one solubility-switching compound; at least one photoinitiator; and at least one solvent, and that can form a film that exhibits a dissolution rate of more than about 0.15 μm / sec when cyclopentanone is used as a developer.

[0004] Patent Documents 2 and 3 also describe photosensitive resin compositions containing a polyamide resin and / or a polyimide resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 172092 [Patent Document 2] International Publication No. 2007 / 047384 [Patent Document 3] JP 2018-070829 A Summary of the Invention [Problem to be solved by the invention]

[0006] When a cured film is formed in an electronic device using a photosensitive resin composition, a curing process using heat is usually performed. Specifically, the photosensitive resin composition is first applied onto a substrate to form a film, and the film is patterned by exposure and development. The patterned film is then heat-treated to form a cured film. As a result of investigations by the present inventors, there was room for further improvement in the extensibility of the cured film and the focus margin in the exposure step and development step described above.

[0007] The present invention has been made in view of the above circumstances. One object of the present invention is to provide a photosensitive resin composition having a large focus margin while having appropriate elongation. [Means for solving the problem]

[0008] The present inventors have completed the invention provided below and have solved the above problems.

[0009] According to the present invention, A polyimide resin (A); A polyfunctional (meth)acrylate compound (B); A photosensitizer (C); A polymerization inhibitor (D); A photosensitive resin composition comprising: The polyimide resin (A) includes a structure represented by the following general formula (a): [ka] In general formula (a), X is a divalent organic group; Y is a tetravalent organic group; A photosensitive resin composition is provided.

[0010] Further, according to the present invention, a film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition; an exposure step of exposing the photosensitive resin film to light; a developing step of developing the exposed photosensitive resin film; A method for manufacturing an electronic device is provided, comprising:

[0011] Further, according to the present invention, There is provided an electronic device comprising a cured film of the above photosensitive resin composition.

[0012] Further, according to the present invention, A light-emitting element; Wiring electrically connected to the light-emitting element; an insulating film covering the wiring; Equipped with There is provided an optical device, wherein the insulating film is a cured film of the above-mentioned photosensitive resin composition. Effect of the Invention

[0013] According to the present invention, there is provided a photosensitive resin composition having a large focus margin while having appropriate elongation properties. [Brief description of the drawings]

[0014] [Figure 1] 1 is a vertical cross-sectional view showing an example of a configuration of an electronic device according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a partial enlarged view of the area surrounded by the dashed line in FIG. [Diagram 3] 2A to 2C are process diagrams illustrating a method for manufacturing the electronic device shown in FIG. [Figure 4] 2A to 2C are diagrams for explaining a method for manufacturing the electronic device shown in FIG. [Diagram 5] 2A to 2C are diagrams for explaining a method for manufacturing the electronic device shown in FIG. [Figure 6] 2A to 2C are diagrams for explaining a method for manufacturing the electronic device shown in FIG. [Figure 7] 1A to 1C are diagrams for explaining a method for manufacturing an optical device according to the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In all drawings, similar components are given similar symbols and descriptions thereof are omitted where appropriate. In order to avoid complexity, (i) when there are multiple identical components in the same drawing, only one of them will be given a reference symbol, and not all of them, or (ii) especially in Figure 2 and subsequent figures, components similar to those in Figure 1 will not be given a reference symbol again. All drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to the actual objects.

[0016] In this specification, the term "approximately" means that a range taking into consideration manufacturing tolerances, assembly variations, and the like, is included, unless otherwise specified explicitly. In this specification, unless otherwise specified, the expression "X to Y" in the explanation of a numerical range means from X to Y. For example, "1 to 5% by mass" means "from 1% by mass to 5% by mass".

[0017] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In this specification, the term "organic group" means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound. In this specification, the term "electronic device" is used to include elements, devices, final products, etc. to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information and communication terminals, light-emitting diodes, physical batteries, and chemical batteries.

[0018] <Photosensitive resin composition> The photosensitive resin composition of the present embodiment contains a polyimide resin (A), a polyfunctional (meth)acrylate compound (B), a photosensitizer (C), and a polymerization inhibitor (D). In the present embodiment, the polyimide resin (A) is a ring-closed polyimide resin containing a ring-closed imide structure represented by the following general formula (a).

[0019] [ka]

[0020] In general formula (a), X is a divalent organic group, and Y is a tetravalent organic group.

[0021] Many of the conventional polyamide / polyimide-based photosensitive resin compositions contain polyamide but not polyimide before use (before a cured film is formed). That is, conventionally, a film is formed on a substrate using a photosensitive resin composition containing polyamide, and the film is typically heated to ring-close the polyamide to form a polyimide. In this case, however, the film shrinks due to the ring-closing reaction and the associated dehydration, making it difficult to obtain a cured film with good flatness.

[0022] On the other hand, the photosensitive resin composition of this embodiment already contains a polyimide resin (A) before use (before forming a cured film). In addition, in this embodiment, a polymerization reaction of a multifunctional (meth)acrylate compound (B) is adopted as the curing mechanism (this polymerization reaction does not, in principle, involve dehydration). Due to these points, by forming a cured film using the photosensitive resin composition of this embodiment, it is possible to form a cured film that has little shrinkage due to heating and has good flatness. In particular, it is possible to form a cured film with good flatness even on a substrate having steps.

[0023] Furthermore, by using the photosensitive resin composition of the present embodiment, it is easy to form a cured film having good heat resistance and mechanical properties (for example, tensile elongation). Cured films in electronic devices are often required to have high heat resistance and good mechanical properties. However, in the past, when resins were designed to be rigid in order to increase heat resistance, the resin lost its flexibility, which could result in reduced mechanical properties such as extensibility. Although the details are unclear, it is believed that in the photosensitive resin composition of this embodiment, the polyfunctional (meth)acrylate compound (B) becomes intricately entangled with the polyimide resin (A) during curing (polymerization), resulting in the formation of a cured film different from conventional cured films. This "intertwining structure of the polyimide resin and the polyfunctional (meth)acrylate" is related to the good heat resistance and good mechanical properties.

[0024] When the polyfunctional (meth)acrylate compound (B) is used, the elongation of the resulting photosensitive resin composition is good as described above, but on the other hand, there is a possibility that swelling of the cured part, insufficient dissolution (bridge) due to uneven dissolution of the unexposed part, and a phenomenon in which the unexposed part is not completely dissolved and remains (foot) may occur. The occurrence of these defects may result in insufficient focus margin. Here, as a result of the study by the present inventors, it was found that it is possible to achieve both good elongation and good focus margin by using the photosensitizer (C) and the polymerization inhibitor (D). In the photosensitive resin composition of this embodiment, the curability of the exposed part is improved by using the photosensitizer (C), and the occurrence of bridges in the development process can be suppressed while maintaining good mechanical properties. In addition, in the photosensitive resin composition of this embodiment, the solubility of the unexposed part is improved by using the polymerization inhibitor (D), and the occurrence of feet in the development process can be suppressed while maintaining good mechanical properties. By highly suppressing these bridges and feet, the focus margin of the photosensitive resin composition can be increased. In other words, by using the photosensitizer (C) and the polymerization inhibitor (D) simultaneously and precisely controlling the ratio between them, it is possible to achieve both good elongation and good focus margin in the cured film of the photosensitive resin composition of this embodiment.

[0025] For the reasons mentioned above, the photosensitive resin composition of the present embodiment is preferably used for forming an insulating layer in an electronic device or an optical device.

[0026] The components that can be contained in the photosensitive resin composition of the present embodiment, and the properties and physical characteristics of the photosensitive resin composition of the present embodiment will be described below.

[0027] (Polyimide resin (A)) The photosensitive resin composition of the present embodiment contains a polyimide resin (A) that includes a structural unit represented by general formula (a).

[0028] [ka]

[0029] In general formula (a), X is a divalent organic group, and Y is a tetravalent organic group.

[0030] As already mentioned, the photosensitive resin composition of the present embodiment tends to shrink less due to curing (heating) by using a polyimide resin containing a closed-ring imide structure represented by general formula (a) before curing.

[0031] When the number of moles of imide groups contained in the polyimide resin (A) is IM and the number of moles of amide groups contained in the polyimide resin (A) is AM, the imidization rate represented by {IM / (IM+AM)}×100(%) is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more. In other words, it is preferable that the polyimide resin (A) is a resin that has no or few open amide structures and many closed imide structures. By using such a polyimide, it is possible to further suppress shrinkage due to heating and form a cured film with better flatness. The imidization rate can be known, for example, from the area of ​​a peak corresponding to an amide group or the area of ​​a peak corresponding to an imide group in an NMR spectrum, etc. As another example, the imidization rate can be known from the area of ​​a peak corresponding to an amide group or the area of ​​a peak corresponding to an imide group in an infrared absorption spectrum, etc.

[0032] The polyimide resin (A) preferably contains a polyimide resin containing fluorine atoms. As the inventors have found, the polyimide resin containing fluorine atoms tends to have better solubility in organic solvents than the polyimide resin not containing fluorine atoms. Therefore, by using the polyimide resin containing fluorine atoms, the photosensitive resin composition is easily made into a varnish-like state. The amount (mass ratio) of fluorine atoms in the fluorine-containing polyimide resin is, for example, 1 to 30 mass%, preferably 3 to 28 mass%, and more preferably 5 to 25 mass%. By containing a certain amount of fluorine atoms in the polyimide resin, sufficient organic solvent solubility is easily obtained. On the other hand, from the viewpoint of balance with other performances, it is preferable that the amount of fluorine atoms is not too large.

[0033] By designing the terminals of the polyimide resin (A) in various ways, for example, the mechanical properties (such as tensile elongation) of the cured product can be further improved.

[0034] For example, the polyimide resin (A) preferably has a group at its terminal that can react with an epoxy group to form a bond, such as an acid anhydride group, a hydroxyl group, an amino group, or a carboxyl group.

[0035] Preferably, the polyimide resin (A) has an acid anhydride group at its terminal. In the photosensitive resin composition of this embodiment, the acid anhydride group and the epoxy group easily form a bond. The acid anhydride group is preferably a group having an acid anhydride skeleton with a cyclic structure. The "cyclic structure" here is preferably a 5-membered or 6-membered ring, more preferably a 5-membered ring.

[0036] In the structural unit represented by general formula (a) constituting the polyimide resin (A), X is a divalent organic group and Y is a tetravalent organic group.

[0037] The divalent organic group of X and / or the tetravalent organic group of Y preferably contain an aromatic ring structure, more preferably a benzene ring structure, which tends to further increase heat resistance. The divalent organic group of X and / or the tetravalent organic group of Y preferably have a structure in which 2 to 6 benzene rings are bonded via a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a fluorinated alkylene group, and an ether group. The alkylene group and the fluorinated alkylene group may be linear or branched. The divalent organic group for X has 6 to 30 carbon atoms, for example. The tetravalent organic group for Y has 6 to 20 carbon atoms, for example. Each of the two imide rings in general formula (a) is preferably a five-membered ring.

[0038] The polyimide resin (A) preferably contains a polyimide resin containing fluorine atoms, which tends to increase the solubility in organic solvents. From the viewpoint of further improving the solubility in organic solvents, it is preferable that both X and Y are fluorine atom-containing groups.

[0039] The polyimide resin (A) more preferably contains a structural unit represented by the following general formula (aa).

[0040] [ka]

[0041] In general formula (aa), Y' represents a single bond or an alkylene group; X has the same meaning as X in formula (a). The alkylene group of Y' may be linear or branched. It is preferable that some or all of the hydrogen atoms of the alkylene group of Y' are substituted with fluorine atoms. The number of carbon atoms of the alkylene group of Y' is, for example, 1 to 6, preferably 1 to 4, and more preferably 1 to 3.

[0042] The polyimide resin (A) can typically be obtained by (i) first synthesizing a polyamide by reacting (condensation polymerization) a diamine with an acid dianhydride, (ii) then imidizing the polyamide (ring-closing reaction), and (iii) introducing a desired functional group into the polymer terminal as necessary. For specific reaction conditions, the examples below and the description in Patent Document 1 above can be referred to.

[0043] In the final polyimide resin (A), the diamine is incorporated into the polymer as the divalent organic group X in the general formula (a), and the acid dianhydride is incorporated into the polymer as the tetravalent organic group Y in the general formula (a). In the synthesis of the polyimide resin (A), one or more diamines can be used, and one or more acid dianhydrides can be used.

[0044] Examples of the diamine raw material include 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 3,3'dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, and 2,2'-bis(p-aminophenyl)hexafluorophosphate. 2,2'-bis(pentafluoroethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy) Benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminobenzotrifluoride (3,5-DAB) TF), 3,5-diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethylbenzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)xanthene (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenylxanthene (3FCDAM), 3,6-diamino-9,9-diphenylxanthene

[0045] Examples of the raw acid dianhydride include pyromellitic anhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA), etc. Of course, the acid dianhydride that can be used is not limited to these. One or more types of acid dianhydride can be used.

[0046] The ratio of the diamine and the acid dianhydride used is basically 1:1 in terms of molar ratio. However, in order to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using an excess of diamine, the terminals (both terminals) of the polyimide resin (A) tend to become amino groups. On the other hand, by using an excess of acid dianhydride, the terminals (both terminals) of the polyimide resin (A) tend to become acid anhydride groups. As described above, in this embodiment, it is preferable that the polyimide resin (A) has an acid anhydride group at its terminal. Therefore, in this embodiment, it is preferable to use an excess of acid dianhydride when synthesizing the polyimide resin (A).

[0047] The amino group and / or acid anhydride group at the end of the polyimide obtained by condensation polymerization may be reacted with a certain reagent so that the polyimide end has a desired functional group.

[0048] The weight average molecular weight of the polyimide resin (A) is, for example, 5,000 to 100,000, preferably 7,000 to 75,000, and more preferably 10,000 to 50,000. When the weight average molecular weight of the polyimide resin (A) is relatively large, for example, a cured film having sufficient heat resistance can be obtained. In addition, when the weight average molecular weight of the polyimide resin (A) is not too large, the polyimide resin (A) can be easily dissolved in an organic solvent. The weight average molecular weight can usually be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0049] (Polyfunctional (meth)acrylate compound (B)) The photosensitive resin composition of the present embodiment contains a polyfunctional (meth)acrylate compound (B). The polyfunctional (meth)acrylate compound (B) may be, without particular limitation, a compound having two or more (meth)acryloyl groups in one molecule.

[0050] From the viewpoint of realizing the above-mentioned "intertwined structure of polyimide resin and polyfunctional (meth)acrylate" and from the viewpoint of obtaining a strong cured film with good chemical resistance, the polyfunctional (meth)acrylate compound (B) is preferably trifunctional or more. There is no particular upper limit to the number of functional groups of the polyfunctional (meth)acrylate compound (B), but from the viewpoint of ease of obtaining raw materials, the upper limit to the number of functional groups is, for example, 11 functional groups. Generally speaking, when a polyfunctional (meth)acrylate compound (B) having a large number of functional groups ((meth)acryloyl groups) is used, the chemical resistance of the cured film tends to be improved. On the other hand, when a polyfunctional (meth)acrylate compound (B) having a small number of functional groups ((meth)acryloyl groups) is used, the mechanical properties of the cured film, such as the tensile elongation, tend to be good.

[0051] As an example, the polyfunctional (meth)acrylate compound (B) preferably contains a tri- or tetrafunctional (meth)acrylate compound (B1).

[0052] As an example, the polyfunctional (meth)acrylate compound (B) preferably contains a pentafunctional or higher (meth)acrylate compound (B2).

[0053] As an example, the polyfunctional (meth)acrylate compound (B) may include a compound represented by the following general formula (b): In the following general formula, R' is a hydrogen atom or a methyl group, n is 0 to 3, and R is a hydrogen atom or a (meth)acryloyl group.

[0054] [ka]

[0055] Specific examples of the polyfunctional (meth)acrylate compound (B) include the following: Of course, the polyfunctional (meth)acrylate compound (B) is not limited to these.

[0056] Polyol polyacrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; epoxy acrylates such as di(meth)acrylate of bisphenol A diglycidyl ether and di(meth)acrylate of hexanediol diglycidyl ether, etc.; urethane (meth)acrylates obtained by the reaction of polyisocyanate with a hydroxyl group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate, etc.

[0057] Commercially available products include Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (manufactured by Toa Gosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat #230, Viscoat #300, Viscoat #802, Viscoat #2500, Viscoat #1000, Viscoat #1080 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-BPE-10, NK Ester A-GLY-9E, NK Ester A-9550, NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0058] The photosensitive resin composition may contain only one polyfunctional (meth)acrylate compound (B), or may contain two or more polyfunctional (meth)acrylate compounds (B). In the latter case, it is preferable to use polyfunctional (meth)acrylate compounds (B) having different numbers of functional groups in combination. By using polyfunctional (meth)acrylate compounds (B) having different numbers of functional groups in combination, a more complex "intertwined structure of polyimide and polyfunctional (meth)acrylate" is formed, and it is believed that better heat resistance and mechanical properties can be obtained. Incidentally, among commercially available polyfunctional (meth)acrylate compounds (B), there are mixtures of (meth)acrylates having different numbers of functional groups.

[0059] The amount of the polyfunctional (meth)acrylate compound (B) relative to 100 parts by mass of the polyimide resin (A) is, for example, 25 to 150 parts by mass, preferably 50 to 120 parts by mass, more preferably 70 to 100 parts by mass, and further preferably 80 to 95 parts by mass. The amount of the polyfunctional (meth)acrylate compound (B) used is not particularly limited, but by appropriately adjusting the amount used as described above, one or more of the various performances can be further improved. As described above, in the photosensitive resin composition of this embodiment, it is considered that an "entanglement structure of polyimide having a cyclic structure and polyfunctional (meth)acrylate" is formed by curing, and by appropriately adjusting the amount of the polyfunctional (meth)acrylate compound (B) used relative to the polyimide resin (A), the polyimide resin (A) and the polyfunctional (meth)acrylate compound (B) are sufficiently entangled, and the amount of excess components not involved in the entanglement is reduced, resulting in further improved performance.

[0060] (Photosensitizer (C)) The photosensitive resin composition of the present embodiment contains a photosensitizer (C). The photosensitizer (C) is not particularly limited as long as it is capable of generating an active species by light and curing the photosensitive resin composition.

[0061] The photosensitizer (C) preferably contains a photoradical generator, which is particularly effective for polymerizing the polyfunctional (meth)acrylate compound (B).

[0062] The photoradical generator that can be used is not particularly limited, and any known photoradical generator can be used as appropriate. For example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophene alkylphenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzoin, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl benzoin compounds such as benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxy ... halomethylated triazine compounds such as 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2- Examples of suitable oxime ester compounds include bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium and the like; acylphosphine compounds such as acylphosphine oxide and the like; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid and the like; and acridine compounds such as 9-phenylacridine and the like. Among these, oxime ester compounds can be particularly preferably used.

[0063] The photosensitive resin composition may contain only one type of photosensitizer (C), or may contain two or more types. The content of the photosensitizer (C) is, for example, 5 parts by mass or more and 30 parts by mass or less, and preferably 10 parts by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the polyimide resin (A).

[0064] (Polymerization inhibitor (D)) The photosensitive resin composition of the present embodiment contains a polymerization inhibitor (D). In the present embodiment, examples of the polymerization inhibitor (D) include hindered phenol compounds, hindered amine compounds, N-oxyl compounds, and thioether compounds. Among these, it is preferable to include one or more selected from hindered phenol compounds, hindered amine compounds, and N-oxyl compounds from the viewpoint of improving the solubility of the unexposed area.

[0065] Examples of the hindered phenol compounds include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene di-m-cresol, pentaerythritol tetrakis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethyl 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1035), N,N'-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide], bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylene bis(oxyethylene)], 1,6 -Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-cresol, 2,4-bis[(dodecylthio)methyl]-6-methylphenol (Irganox1726), 2,4-bis(octylthiomethyl)-6-methylphenol (Irganox1520L), etc. These may be used alone or in combination of two or more.

[0066] Examples of the hindered amine compounds include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy- Examples of the esters include a mixture of 1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane and bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, and a reaction product of 2,2,6,6-tetramethylpiperidin-4-ylhexadecanoate and 2,2,6,6-tetramethylpiperidin-4-yloctadecanoate. These may be used alone or in combination of two or more.

[0067] Examples of N-oxyl compounds include 4-benzoyloxy-2,2,6,6-tetramethylpiperidinooxyl (4-benzoyloxy TEMPO), N-nitrosodiphenylamine, N-nitroso-N-phenylhydroxylamine, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidi-1-oxyl free radical (4-hydroxy TEMPO), bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate (bisTEMPO sebacate), etc. These may be used alone or in combination of two or more.

[0068] Examples of the thioether compounds include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], di(tridecyl)-3,3'-thiodipropionate, etc. These may be used alone or in combination of two or more.

[0069] In the photosensitive resin composition of the present embodiment, the content of the polymerization inhibitor (D) relative to 100 parts by mass of the polyimide resin (A) is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 1 part by mass or more and 3 parts by mass or less. If the content of the polymerization inhibitor (D) is within the above range, the solubility of the unexposed area is improved, and the occurrence of a phenomenon (foot) in which the unexposed area is not completely dissolved and remains in the development process can be suppressed while maintaining good mechanical properties.

[0070] In the photosensitive resin composition of this embodiment, the content of the polymerization inhibitor (D) relative to 100 parts by mass of the photosensitizer (C) is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less. If the content of the polymerization inhibitor (D) relative to 100 parts by mass of the photosensitizer (C) is within the above range, it is possible to achieve both good elongation and good focus margin in the cured film of the photosensitive resin composition of this embodiment.

[0071] (Thermal Radical Generator (E)) The photosensitive resin composition of the present embodiment preferably contains a thermal radical generator (E). By using the thermal radical generator (E), for example, the heat resistance of the cured film can be further increased, and / or the chemical resistance (resistance to organic solvents, etc.) of the cured film can be increased. This is believed to be because the polymerization reaction of the polyfunctional (meth)acrylate compound (B) is further promoted by using the thermal radical generator (E).

[0072] The thermal radical generator (E) preferably comprises an organic peroxide. Examples of organic peroxides include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, parachlorobenzoyl peroxide, and cyclohexanone peroxide.

[0073] When a thermal radical generator (E) is used, only one thermal radical generator (E) may be used, or two or more thermal radical generators (E) may be used. When the thermal radical generator (E) is used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polyimide resin (A).

[0074] (Crosslinking agent (F)) The photosensitive resin composition of the present embodiment preferably contains a crosslinking agent (F). By using the crosslinking agent (F), for example, the crosslinking agent (F) reacts with other components contained in the photosensitive resin composition, or the crosslinking agents (F) polymerize with each other, so that the crosslinking agent (F) becomes closely intertwined with the photosensitive resin composition. This is thought to improve the chemical resistance and elongation of the resin film made of the cured product of the photosensitive resin composition.

[0075] The crosslinking agent (F) preferably has an epoxy-containing group at one end of the molecule and a (meth)acryloyl group at the other end. This configuration reduces unreacted functional groups, resulting in improved chemical resistance and extensibility of the resin film made of the cured product of the photosensitive resin composition.

[0076] In this embodiment, the term "epoxy-containing group" refers to a substituent having a three-membered ring ether, oxacyclopropane (oxirane), in the structural formula. Specific examples thereof include epoxy groups, glycidyl groups, glycidyl ether groups, and groups in which one or more hydrogen atoms in an organic group are substituted with epoxy groups, glycidyl groups, or glycidyl ether groups (groups in which hydrogen has been removed from the OH group of glycidol), and specifically, a 1,2-epoxycyclohexyl group can be mentioned. The organic group is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; alkenyl groups such as allyl, pentenyl, and vinyl groups; alkynyl groups such as ethynyl groups; alkylidene groups such as methylidene and ethylidene groups; aryl groups such as phenyl, naphthyl, and anthracenyl groups; aralkyl groups such as benzyl and phenethyl groups; alkaryl groups such as tolyl and xylyl groups; and cycloalkyl groups such as adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0077] The crosslinking agent (F) preferably contains a compound represented by general formula (1).

[0078] [ka]

[0079] In the general formula (1), X1 represents a (meth)acryloyl group, X2 represents an epoxy-containing group such as a glycidyl group, a glycidyl ether group, an epoxy group, or a 1,2-epoxycyclohexyl group, and n represents an integer of 1 to 10.

[0080] By selecting X2 from the above functional groups, the reactivity between the crosslinking agent (F) and other components contained in the photosensitive resin composition or between the crosslinking agents (F) themselves becomes good, and the chemical resistance and elongation of the resin film made of the cured product of the photosensitive resin composition are improved, which is preferable.

[0081] Furthermore, it is preferable that n is within the range of 1 to 10, since this results in a more suitable elongation percentage of the resin film made of the cured product of the photosensitive resin composition.

[0082] In the crosslinking agent (F), it is preferable to include one or more compounds selected from any of the compounds represented by the following chemical formulas (2) to (4) as a compound satisfying the above general formula (1). By including one or more compounds selected from any of the compounds represented by the following chemical formulas (2) to (4), it is possible to achieve a high balance between the chemical resistance and elongation of the resin film made of the cured product of the photosensitive resin composition.

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] The content of the crosslinking agent (F) is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and more preferably 1 part by mass or more, based on 100 parts by mass of the polyimide resin (A). By having the content of the crosslinking agent (F) of 0.1 part by mass or more, the cured product of the photosensitive resin composition can have high chemical resistance. The content of the crosslinking agent (F) is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the polyimide resin (A). By making the content of the crosslinking agent (F) 30 parts by mass or less, the ratio of the polyimide resin (A) in the photosensitive resin composition is maintained, the elongation percentage of the cured product of the photosensitive resin composition becomes good, and the adhesion between the photosensitive resin composition and the substrate is sufficiently improved.

[0087] The photosensitive resin composition of the present embodiment may contain only one type of crosslinking agent (F), or may contain two or more types.

[0088] (Silane coupling agent (G)) The photosensitive resin composition of the present embodiment preferably contains a silane coupling agent (G). By using the silane coupling agent (G), for example, the adhesion between the substrate and the cured film can be further improved.

[0089] Examples of the silane coupling agent (G) that can be used include amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, (meth)acryloyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, vinyl group-containing silane coupling agents, ureido group-containing silane coupling agents, sulfide group-containing silane coupling agents, and silane coupling agents having a cyclic anhydride structure.

[0090] Examples of amino group-containing silane coupling agents include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane. Examples of epoxy group-containing silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidylpropyltrimethoxysilane. Examples of the (meth)acryloyl group-containing silane coupling agent include γ-((meth)acryloyloxypropyl)trimethoxysilane, γ-((meth)acryloyloxypropyl)methyldimethoxysilane, and γ-((meth)acryloyloxypropyl)methyldiethoxysilane. An example of the mercapto group-containing silane coupling agent is 3-mercaptopropyltrimethoxysilane. Examples of the vinyl group-containing silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane. An example of the ureido group-containing silane coupling agent is 3-ureidopropyltriethoxysilane. Examples of the sulfide group-containing silane coupling agent include bis(3-(triethoxysilyl)propyl) disulfide, bis(3-(triethoxysilyl)propyl) tetrasulfide, and the like. Examples of the silane coupling agent having a cyclic anhydride structure include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, and 3-dimethylmethoxysilylpropylsuccinic anhydride.

[0091] In this embodiment, a silane coupling agent having a cyclic anhydride structure is preferably used. Although the details are unclear, it is presumed that the cyclic anhydride structure is easily reactive with the main chain, side chain and / or end of the polyimide resin (A), and therefore a particularly good adhesion improving effect can be obtained.

[0092] When the silane coupling agent (G) is used, it may be used alone or two or more kinds of adhesion assistants may be used in combination. When the silane coupling agent (G) is used, the amount used is, for example, 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, more preferably 0.4 to 12 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polyimide resin (A).

[0093] (Curing catalyst (H)) The photosensitive resin composition of the present embodiment preferably contains a curing catalyst (H). This curing catalyst (H) has the function of promoting the reaction of the crosslinking agent (F). By using the curing catalyst (H), the reaction involving the crosslinking agent (F) proceeds sufficiently, and for example, the tensile elongation of the cured film can be further improved.

[0094] Examples of the curing catalyst (H) include compounds known as curing catalysts (often called curing accelerators) for epoxy resins. For example, diazabicycloalkenes such as 1,8-diazabicyclo[5,4,0]undecene-7 and their derivatives; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphines such as triphenylphosphine and methyldiphenylphosphine; tetra-substituted phosphonium salts such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrabenzoic acid borate, tetraphenylphosphonium tetranaphthoic acid borate, tetraphenylphosphonium tetranaphthoyloxyborate, tetraphenylphosphonium tetranaphthyloxyborate, and tetraphenylphosphonium 4,4'-sulfonyldiphenolate; and triphenylphosphine adducted with benzoquinone. Among these, organic phosphines are preferred.

[0095] When the curing catalyst (H) is used, the amount thereof is, for example, 1 to 80 parts by mass, preferably 2 to 50 parts by mass, and more preferably 3 to 30 parts by mass, relative to 100 parts by mass of the crosslinking agent (F).

[0096] (Surfactant (I)) The photosensitive resin composition of the present embodiment preferably contains a surfactant (I), which can further improve the coatability of the photosensitive resin composition and the flatness of the film. Examples of the surfactant (I) include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic-based surfactants. From another viewpoint, the surfactant is preferably nonionic. The use of a nonionic surfactant is preferable from the viewpoints of, for example, suppressing unintentional reactions with other components in the composition and enhancing the storage stability of the composition.

[0097] The surfactant (I) preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improved coating properties), improving developability, and also improving adhesive strength. For example, such a surfactant is preferably a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. Commercially available products that can be used as the surfactant (I) include, for example, F-251, F-253, F-281, F-430, F-477, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-566, F-567, F-568, F-569, F-570, F-571, F-572, F-573, F-574, F-575, F-576, F-577, F-578, F-579, F-580, F-581, F-582, F-583, F-584, F-585, F-586, F-587, F-588, F-589 ... fluorine-containing oligomer structure surfactants such as F-68, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc.; fluorine-containing nonionic surfactants such as F-tergent 250 and F-tergent 251 manufactured by NEOS Corporation; and silicone surfactants such as the SILFOAM (registered trademark) series manufactured by Wacker Chemie (e.g. SD 100 TS, SD 670, SD 850, SD 860, SD 882). Other preferred surfactants include FC4430 and FC4432 manufactured by 3M.

[0098] When the photosensitive resin composition of the present embodiment contains a surfactant (I), it may contain one or more surfactants. When the photosensitive resin composition of the present embodiment contains the surfactant (I), the amount thereof is, for example, 0.001 to 1 part by mass, and preferably 0.005 to 0.5 parts by mass, relative to 100 parts by mass of the content of the polyimide resin (A).

[0099] (Solvent (J) / Properties of Composition) The photosensitive resin composition of the present embodiment preferably contains a solvent (J), which makes it possible to easily form a photosensitive resin film on a substrate (particularly a substrate having a step) by a coating method. The solvent (J) usually contains an organic solvent. There are no particular limitations on the organic solvent, so long as it can dissolve or disperse the above-mentioned components and does not substantially chemically react with the components.

[0100] Examples of organic solvents include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, γ-butyrolactone, methyl lactate, ethyl lactate, butyl lactate, etc. These may be used alone or in combination.

[0101] When the photosensitive resin composition of this embodiment contains a solvent (J), the photosensitive resin composition of this embodiment is usually in a varnish state. More specifically, the photosensitive resin composition of this embodiment is preferably a varnish-like composition in which at least the polyimide resin (A) and the polyfunctional (meth)acrylate compound (B) are dissolved in the solvent (J). Since the photosensitive resin composition of this embodiment is in a varnish state, a uniform film can be formed by coating. In addition, since the polyimide resin (A) and the polyfunctional (meth)acrylate compound (B) are "dissolved" in the solvent (J), a uniform cured film can be obtained.

[0102] When the solvent (J) is used, it is used so that the concentration of the total solids (non-volatile components) in the photosensitive resin composition is preferably 10 to 50 mass %, more preferably 20 to 45 mass %. By setting the concentration in this range, each component can be sufficiently dissolved or dispersed. In addition, good coatability can be ensured, which in turn leads to improved flatness during spin coating. Furthermore, by adjusting the content of the non-volatile components, the viscosity of the photosensitive resin composition can be appropriately controlled. From another perspective, the ratio of the polyimide resin (A) and the polyfunctional (meth)acrylate compound (B) in the entire composition is preferably 20 to 50 mass %. By using a relatively large amount of the polyimide resin (A) and the polyfunctional (meth)acrylate compound (B), a film of an appropriate thickness can be easily formed.

[0103] (Other Ingredients) In addition to the above components, the photosensitive resin composition of the present embodiment may contain components other than the above components as necessary. Examples of such components include water, a filler such as silica, a sensitizer, a film-forming agent, etc.

[0104] <Electronic device manufacturing method, electronic device> The method for producing an electronic device according to the present embodiment includes the steps of: a film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition; an exposure step of exposing the photosensitive resin film to light; a developing step of developing the exposed photosensitive resin film; Includes. In addition, the method for producing an electronic device according to the present embodiment preferably includes a thermal curing step of heating and curing the exposed photosensitive resin film after the above-mentioned development step, thereby making it possible to obtain a cured film with sufficient heat resistance. In this manner, an electronic device having a cured film of the photosensitive resin composition of the present embodiment can be produced.

[0105] The method for producing the electronic device of this embodiment and the structure of the electronic device including the cured product of the photosensitive resin composition of this embodiment will be described in more detail below with reference to the drawings.

[0106] Fig. 1 is a vertical cross-sectional view showing an example of an electronic device according to the present embodiment, and Fig. 2 is a partial enlarged view of a region surrounded by a chain line in Fig. 1. In the following description, the upper side in FIG. 1 will be referred to as "upper" and the lower side as "lower".

[0107] An electronic device 1 shown in FIG. 1 has a so-called package-on-package structure, which includes a through electrode substrate 2 and a semiconductor package 3 mounted thereon.

[0108] The through electrode substrate 2 comprises an insulating layer 21, a plurality of through wirings 221 penetrating from the upper surface to the lower surface of the insulating layer 21, a semiconductor chip 23 embedded inside the insulating layer 21, a lower wiring layer 24 provided on the lower surface of the insulating layer 21, an upper wiring layer 25 provided on the upper surface of the insulating layer 21, and solder bumps 26 provided on the lower surface of the lower wiring layer 24.

[0109] The semiconductor package 3 includes a package substrate 31, a semiconductor chip 32 mounted on the package substrate 31, bonding wires 33 electrically connecting the semiconductor chip 32 and the package substrate 31, a sealing layer 34 in which the semiconductor chip 32 and the bonding wires 33 are embedded, and solder bumps 35 provided on the underside of the package substrate 31.

[0110] Then, the semiconductor package 3 is laminated on the through electrode substrate 2. As a result, the solder bumps 35 of the semiconductor package 3 and the upper wiring layer 25 of the through electrode substrate 2 are electrically connected to each other.

[0111] In such an electronic device 1, it is possible to easily achieve a low height because there is no need to use a thick substrate such as an organic substrate including a core layer in the through electrode substrate 2. This can also contribute to the miniaturization of electronic devices incorporating the electronic device 1.

[0112] In addition, since the through hole electrode substrate 2 and the semiconductor package 3 each having a different semiconductor chip are stacked, the packaging density per unit area can be increased. This makes it possible to achieve both miniaturization and high performance.

[0113] The through electrode substrate 2 and the semiconductor package 3 will be described in further detail below. 2 includes an insulating layer, a wiring layer, a through-hole wiring, etc. As a result, the lower wiring layer 24 and the upper wiring layer 25 include wiring inside and on the surface, and are electrically connected to each other via the through-hole wiring 221 that penetrates the insulating layer 21.

[0114] The wiring layer included in the lower wiring layer 24 is connected to the semiconductor chip 23 and the solder bumps 26. Therefore, the lower wiring layer 24 functions as a rewiring layer for the semiconductor chip 23, and the solder bumps 26 function as external terminals for the semiconductor chip 23.

[0115] 2 is provided to penetrate the insulating layer 21, as described above. This electrically connects the lower wiring layer 24 and the upper wiring layer 25, and enables the through electrode substrate 2 and the semiconductor package 3 to be stacked, thereby improving the functionality of the electronic device 1.

[0116] 2 is connected to the through-wires 221 and the solder bumps 35. As a result, the upper wiring layer 25 is electrically connected to the semiconductor chip 23 and functions as a rewiring layer for the semiconductor chip 23 and also as an interposer interposed between the semiconductor chip 23 and the package substrate 31. A cured film of the photosensitive resin composition of the present embodiment can be used to form an insulating layer of the rewiring layer.

[0117] According to this embodiment, an electronic device can be realized which comprises a semiconductor chip 23 and a rewiring layer (upper wiring layer 25) provided on the surface of the semiconductor chip 23, and in which an insulating layer in the rewiring layer is composed of a cured product of the photosensitive resin composition of this embodiment.

[0118] The through-hole wiring 221 penetrates the insulating layer 21, thereby providing an effect of reinforcing the insulating layer 21. Therefore, even if the mechanical strength of the lower wiring layer 24 or the upper wiring layer 25 is low, it is possible to avoid a decrease in the mechanical strength of the entire through-hole electrode substrate 2. As a result, the lower wiring layer 24 and the upper wiring layer 25 can be made even thinner, and the height of the electronic device 1 can be made even lower.

[0119] 1 also includes, in addition to the through wiring 221, a through wiring 222 provided so as to penetrate the insulating layer 21 located on the upper surface of the semiconductor chip 23. This allows electrical connection between the upper surface of the semiconductor chip 23 and the upper wiring layer 25.

[0120] The insulating layer 21 is provided so as to cover the semiconductor chip 23. This enhances the effect of protecting the semiconductor chip 23. As a result, the reliability of the electronic device 1 can be improved. In addition, the electronic device 1 can be easily applied to a mounting method such as the package-on-package structure according to the present embodiment.

[0121] The diameter W (see FIG. 2) of the through wire 221 is not particularly limited, but is preferably about 1 to 100 μm, and more preferably about 2 to 80 μm. This ensures the conductivity of the through wire 221 without impairing the mechanical properties of the insulating layer 21.

[0122] The semiconductor package 3 shown in Fig. 1 may be a package of any type, such as a Quad Flat Package (QFP), a Small Outline Package (SOP), a Ball Grid Array (BGA), a Chip Size Package (CSP), a Quad Flat Non-leaded Package (QFN), a Small Outline Non-leaded Package (SON), a Lead Flame BGA (LF-BGA), etc.

[0123] The arrangement of the semiconductor chips 32 is not particularly limited, but as an example, multiple semiconductor chips 32 are stacked in Fig. 1. This increases the packaging density. The multiple semiconductor chips 32 may be arranged side by side in the planar direction, or may be stacked in the thickness direction and arranged side by side in the planar direction.

[0124] The package substrate 31 may be any substrate, but is, for example, a substrate including an insulating layer, a wiring layer, and through-wires (not shown). Among these, the solder bumps 35 and the bonding wires 33 can be electrically connected via the through-wires.

[0125] The sealing layer 34 is made of, for example, a known sealing resin material. By providing such a sealing layer 34, the semiconductor chip 32 and the bonding wires 33 can be protected from external forces and the external environment.

[0126] The semiconductor chip 23 included in the through electrode substrate 2 and the semiconductor chip 32 included in the semiconductor package 3 are disposed close to each other. This provides benefits such as faster intercommunication and lower loss. From this perspective, for example, if one of the semiconductor chip 23 and the semiconductor chip 32 is a computing element such as a CPU (Central Processing Unit), a GPU (Graphics Processing Unit), or an AP (Application Processor), and the other is a storage element such as a DRAM (Dynamic Random Access Memory) or a flash memory, these elements can be disposed close to each other within the same device. This makes it possible to realize an electronic device 1 that is both highly functional and compact.

[0127] Next, a method for manufacturing the electronic device 1 shown in FIG. 1 will be described.

[0128] Fig. 3 is a process diagram showing a method for manufacturing the electronic device 1 shown in Fig. 1. Also, Figs. 4 to 6 are diagrams for explaining the method for manufacturing the electronic device 1 shown in Fig. 1.

[0129] The manufacturing method of the electronic device 1 includes a chip placement process S1 of obtaining an insulating layer 21 so as to embed the semiconductor chip 23 and the through-wires 221, 222 provided on the substrate 202, an upper wiring layer formation process S2 of forming an upper wiring layer 25 on the insulating layer 21 and the semiconductor chip 23, a substrate peeling process S3 of peeling the substrate 202, a lower wiring layer formation process S4 of forming a lower wiring layer 24, a solder bump formation process S5 of forming solder bumps 26 to obtain the through electrode substrate 2, and a stacking process S6 of stacking a semiconductor package 3 on the through electrode substrate 2.

[0130] Among these, the upper wiring layer formation process S2 includes a first resin film arrangement process S20 of arranging a photosensitive resin varnish 5 (a varnish-like photosensitive resin composition) on the insulating layer 21 and the semiconductor chip 23 to obtain a photosensitive resin layer 2510, a first exposure process S21 of performing an exposure process on the photosensitive resin layer 2510, a first development process S22 of performing a development process on the photosensitive resin layer 2510, a first curing process S23 of performing a curing process on the photosensitive resin layer 2510, and a wiring layer formation process S24 of forming the wiring layer 253. The method includes step S24, a second resin film arrangement step S25 of arranging a photosensitive resin varnish 5 on the photosensitive resin layer 2510 and the wiring layer 253 to obtain a photosensitive resin layer 2520, a second exposure step S26 of subjecting the photosensitive resin layer 2520 to an exposure process, a second development step S27 of subjecting the photosensitive resin layer 2520 to a development process, a second curing step S28 of subjecting the photosensitive resin layer 2520 to a curing process, and a through wiring formation step S29 of forming a through wiring 254 in the opening 424 (through hole).

[0131] Each step will be described below in order. The following manufacturing method is an example, and the method is not limited to this.

[0132] [1] Chip placement process S1 First, as shown in FIG. 4(a), a chip-embedded structure 27 is prepared, which includes a substrate 202, a semiconductor chip 23 and through-wires 221, 222 provided on the substrate 202, and an insulating layer 21 provided so as to embed these.

[0133] The constituent material of the substrate 202 is not particularly limited, but examples thereof include metal materials, glass materials, ceramic materials, semiconductor materials, organic materials, etc. Furthermore, the substrate 202 may be a semiconductor wafer such as a silicon wafer, a glass wafer, or the like.

[0134] The semiconductor chip 23 is bonded onto the substrate 202. In this manufacturing method, as an example, a plurality of semiconductor chips 23 are arranged side by side on the same substrate 202 while being spaced apart from each other. The plurality of semiconductor chips 23 may be of the same type or different types. In addition, the substrate 202 and the semiconductor chip 23 may be fixed to each other via an adhesive layer (not shown) such as a die attach film.

[0135] If necessary, an interposer (not shown) may be provided between the substrate 202 and the semiconductor chip 23. The interposer functions as, for example, a rewiring layer for the semiconductor chip 23. Therefore, the interposer may have pads (not shown) for electrically connecting to electrodes of the semiconductor chip 23, which will be described later. This allows the pad spacing and arrangement pattern of the semiconductor chip 23 to be changed, thereby further increasing the design freedom of the electronic device 1. The interposer may be made of, for example, an inorganic substrate such as a silicon substrate, a ceramic substrate, or a glass substrate, or an organic substrate such as a resin substrate.

[0136] The insulating layer 21 may be, for example, a resin film (organic insulating layer) containing a thermosetting resin or a thermoplastic resin such as those listed as components of the photosensitive resin composition, or may be a conventional sealing material used in the semiconductor technology field.

[0137] Examples of materials for the through-wires 221 and 222 include copper or a copper alloy, aluminum or an aluminum alloy, gold or a gold alloy, silver or a silver alloy, nickel or a nickel alloy, and the like.

[0138] It should be noted that the chip-embedded structure 27 may be prepared by a method different from that described above.

[0139] [2] Upper wiring layer formation process S2 Next, an upper wiring layer 25 is formed on the insulating layer 21 and the semiconductor chip 23 .

[0140] [2-1] First resin film placement step S20 First, as shown in Fig. 4(b), a photosensitive resin varnish 5 is applied (placed) on the insulating layer 21 and the semiconductor chip 23. This results in a liquid coating of the photosensitive resin varnish 5 as shown in Fig. 4(c). The photosensitive resin varnish 5 is the photosensitive resin composition of this embodiment.

[0141] The photosensitive resin varnish 5 is applied by using, for example, a spin coater, a bar coater, a spray device, an inkjet device, or the like.

[0142] The viscosity of the photosensitive resin varnish 5 is not particularly limited, but is 10 cP to 6000 cP, preferably 20 cP to 5000 cP, and more preferably 30 cP to 4000 cP. When the viscosity of the photosensitive resin varnish 5 is within the above range, a thinner photosensitive resin layer 2510 (see FIG. 4(d)) can be formed. As a result, the upper wiring layer 25 can be made thinner, and the electronic device 1 can be easily made thinner. The viscosity of the photosensitive resin varnish 5 is, for example, a value measured using a cone-plate type viscometer (TV-25, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 100 rpm.

[0143] Next, the liquid coating of the photosensitive resin varnish 5 is dried, thereby obtaining the photosensitive resin layer 2510 shown in FIG.

[0144] The drying conditions for the photosensitive resin varnish 5 are not particularly limited, but may be, for example, heating at a temperature of 80 to 150° C. for 1 to 60 minutes.

[0145] In this step, a process of disposing a photosensitive resin film obtained by forming the photosensitive resin varnish 5 into a film may be adopted instead of the process of applying the photosensitive resin varnish 5. The photosensitive resin film is the photosensitive resin composition of this embodiment and is a resin film having photosensitivity.

[0146] The photosensitive resin film is produced, for example, by applying a photosensitive resin varnish 5 onto a base such as a carrier film by means of various coating devices, and then drying the resulting coating.

[0147] After the photosensitive resin layer 2510 is formed in this manner, a pre-exposure heat treatment is performed on the photosensitive resin layer 2510 as necessary. By performing the pre-exposure heat treatment, the molecules contained in the photosensitive resin layer 2510 are stabilized, and the reaction in the first exposure step S21 described below can be stabilized. On the other hand, by heating under the heating conditions described below, adverse effects of heating on the photoacid generator can be minimized.

[0148] The temperature of the pre-exposure bake is preferably 70 to 130° C., more preferably 75 to 120° C., and even more preferably 80 to 110° C. If the temperature of the pre-exposure bake is below the lower limit, the purpose of stabilizing the molecules by the pre-exposure bake may not be achieved. On the other hand, if the temperature of the pre-exposure bake is above the upper limit, the movement of the photoacid generator becomes too active, and the effect of making it difficult to generate acid even when irradiated with light in the first exposure step S21 described below may become widespread, resulting in a decrease in the processing accuracy of patterning.

[0149] The time of pre-exposure heat treatment is appropriately set according to the temperature of the pre-exposure heat treatment, and is preferably 1 to 10 minutes, more preferably 2 to 8 minutes, and even more preferably 3 to 6 minutes at the above temperature. If the time of pre-exposure heat treatment is below the lower limit, the heating time is insufficient, and the purpose of stabilizing the molecules by the pre-exposure heat treatment may not be achieved. On the other hand, if the time of pre-exposure heat treatment is above the upper limit, the heating time is too long, and even if the temperature of the pre-exposure heat treatment is within the above range, the action of the photoacid generator may be inhibited.

[0150] The atmosphere for the heat treatment is not particularly limited, and may be an inert gas atmosphere or a reducing gas atmosphere, but is preferably air in consideration of work efficiency, etc.

[0151] The atmospheric pressure is not particularly limited. It may be reduced pressure or increased pressure, but normal pressure is used in consideration of work efficiency, etc. Note that normal pressure refers to a pressure of about 30 to 150 kPa, and is preferably atmospheric pressure.

[0152] [2-2] First exposure process S21 Next, the photosensitive resin layer 2510 is subjected to an exposure process.

[0153] 4(d), a mask 412 is placed in a predetermined region on the photosensitive resin layer 2510. Then, light (active radiation) is irradiated through the mask 412. As a result, the photosensitive resin layer 2510 is subjected to an exposure process according to the pattern of the mask 412.

[0154] 4(d) illustrates a case where the photosensitive resin layer 2510 has so-called negative photosensitivity. In this example, the regions of the photosensitive resin layer 2510 that correspond to the light-shielding parts of the mask 412 dissolve in a developer.

[0155] On the other hand, active chemical species are generated from the photosensitive agent (C) in the regions corresponding to the transmitting portions of the mask 412. The active chemical species act as a catalyst for the curing reaction.

[0156] The exposure dose in the exposure treatment is not particularly limited. 2 is preferable, and 200 to 1000 mJ / cm 2 This makes it possible to suppress underexposure and overexposure in the photosensitive resin layer 2510. As a result, high patterning accuracy can be finally achieved. Thereafter, if necessary, the photosensitive resin layer 2510 is subjected to post-exposure heat treatment.

[0157] The temperature of the post-exposure heat treatment is not particularly limited. It is preferably 50 to 150°C, more preferably 50 to 130°C, further preferably 55 to 120°C, and particularly preferably 60 to 110°C. By carrying out the post-exposure heat treatment at such a temperature, the catalytic action of the generated acid is sufficiently enhanced, and the thermosetting resin can be reacted sufficiently in a shorter time. By setting the temperature within the above range, it is possible to suppress a decrease in the processing accuracy of the patterning due to the promotion of acid diffusion. By setting the temperature of the post-exposure bake treatment to the above lower limit, the reaction rate of the thermosetting resin can be increased, and the productivity can be improved. On the other hand, by setting the temperature of the post-exposure bake treatment to the above upper limit, the deterioration of the processing accuracy of the patterning due to the promotion of acid diffusion can be suppressed.

[0158] The time of the post-exposure bake treatment is appropriately set according to the temperature of the post-exposure bake treatment. At the above temperature, the time is preferably 1 to 30 minutes, more preferably 2 to 20 minutes, and further preferably 3 to 15 minutes. By carrying out the post-exposure bake treatment for such a time, the thermosetting resin can be sufficiently reacted, and the diffusion of the acid can be suppressed, thereby suppressing a decrease in the processing accuracy of the patterning.

[0159] The atmosphere for the post-exposure heat treatment is not particularly limited, and may be an inert gas atmosphere or a reducing gas atmosphere, but is preferably air in consideration of work efficiency, etc.

[0160] The atmospheric pressure of the post-exposure heat treatment is not particularly limited. It may be reduced pressure or pressurized pressure, but considering the working efficiency, normal pressure is used. This allows the pre-exposure heat treatment to be performed relatively easily. Note that normal pressure refers to a pressure of about 30 to 150 kPa, and is preferably atmospheric pressure.

[0161] [2-3] First development step S22 Next, a development process is performed on the photosensitive resin layer 2510. As a result, openings 423 penetrating the photosensitive resin layer 2510 are formed in the regions corresponding to the light-shielding portions of the mask 412 (see FIG. 5(e)).

[0162] Examples of the developer include organic developers and water-soluble developers. In this embodiment, the developer preferably contains an organic solvent. More specifically, the developer is preferably a developer whose main component is an organic solvent (a developer whose components are 95% by mass or more of an organic solvent). By developing with a developer containing an organic solvent, it becomes possible to suppress swelling of the pattern caused by the developer, compared to the case of developing with an alkaline developer (aqueous). In other words, a finer pattern is easily obtained.

[0163] Specific examples of organic solvents that can be used in the developer include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether-based solvents such as propylene glycol monomethyl ether. As the developer, an organic solvent developer may be used that is made of only an organic solvent and does not contain any impurities other than those that are inevitably contained. Although the inevitably contained impurities include metal elements and moisture, from the viewpoint of preventing contamination of electronic devices, it is better to have as few inevitably contained impurities as possible.

[0164] There is no particular limitation on the method for bringing the developer into contact with the photosensitive resin layer 2510. Generally known methods such as immersion, paddle, and spray methods can be appropriately applied.

[0165] The time for the development step is usually within the range of about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the thickness of the resin film, the shape of the pattern to be formed, and the like.

[0166] [2-4] First curing step S23 After the development process, the photosensitive resin layer 2510 is subjected to a curing process (post-development heat treatment). The conditions for the curing process are not particularly limited, but are set at a heating temperature of about 160 to 250° C. for a heating time of about 30 to 240 minutes. This makes it possible to cure the photosensitive resin layer 2510 while suppressing the thermal effect on the semiconductor chip 23, and obtain the organic insulating layer 251.

[0167] [2-5] Wiring layer formation step S24 Next, the wiring layer 253 is formed on the organic insulating layer 251 (see FIG. 5(f)). The wiring layer 253 is formed by obtaining a metal layer using a vapor phase deposition method such as a sputtering method or a vacuum deposition method, and then patterning the metal layer using a photolithography method and an etching method. Prior to the formation of the wiring layer 253, a surface modification treatment such as a plasma treatment may be performed.

[0168] [2-6] Second resin film placement step S25 5(g), a photosensitive resin layer 2520 is obtained in the same manner as in the first resin film disposing step S20. The photosensitive resin layer 2520 is disposed so as to cover the wiring layer 253. Thereafter, if necessary, a pre-exposure heat treatment is performed on the photosensitive resin layer 2520. The treatment conditions are, for example, the conditions described in the first resin film disposing step S20.

[0169] [2-7] Second exposure process S26 Next, an exposure process is performed on the photosensitive resin layer 2520. The process conditions are, for example, the conditions described in the first exposure step S21. Thereafter, if necessary, a post-exposure heat treatment is performed on the photosensitive resin layer 2520. The treatment conditions are, for example, the conditions described in the first exposure step S21.

[0170] [2-8]Second development step S27 Next, a development process is performed on the photosensitive resin layer 2520. The process conditions are, for example, the conditions described in the first development step S22. As a result, an opening 424 penetrating the photosensitive resin layers 2510 and 2520 is formed (see FIG. 5(h)).

[0171] [2-9]Second curing step S28 After the development process, the photosensitive resin layer 2520 is subjected to a curing process (post-development heat treatment). The curing conditions are, for example, the conditions described in the first curing step S23. This causes the photosensitive resin layer 2520 to cure, and the organic insulating layer 252 is obtained (see FIG. 6(i)).

[0172] In this embodiment, the upper wiring layer 25 has two layers, the organic insulating layer 251 and the organic insulating layer 252, but may have three or more layers. In this case, after the second curing step S28, a series of steps from the wiring layer forming step S24 to the second curing step S28 may be repeatedly added.

[0173] [2-10]Through wiring formation process S29 Next, the through wiring 254 shown in FIG.

[0174] The through wiring 254 can be formed by a known method, for example, the following method.

[0175] First, a seed layer (not shown) is formed on the organic insulating layer 252. The seed layer is formed on the inner surfaces (side surfaces and bottom surfaces) of the opening 424 and on the upper surface of the organic insulating layer 252. The seed layer may be, for example, a copper seed layer, and may be formed by, for example, a sputtering method. The seed layer may be made of the same metal as the through-wiring 254 to be formed, or may be made of a different metal.

[0176] Next, a resist layer (not shown) is formed on the seed layer (not shown) in a region other than the opening 424. Then, using this resist layer as a mask, the opening 424 is filled with a metal. For example, electrolytic plating is used for this filling. Examples of the metal to be filled include copper or a copper alloy, aluminum or an aluminum alloy, gold or a gold alloy, silver or a silver alloy, nickel or a nickel alloy, etc. In this way, the conductive material is embedded in the opening 424, and the through wiring 254 is formed.

[0177] Next, the resist layer (not shown) is removed, and further, the seed layer (not shown) on the organic insulating layer 252 is removed. For this purpose, for example, a flash etching method can be used. The location where the through wiring 254 is formed is not limited to the location shown in the figure.

[0178] [3] Substrate peeling process S3 6(j), the substrate 202 is peeled off, thereby exposing the lower surface of the insulating layer 21.

[0179] [4] Lower wiring layer formation step S4 6(k), a lower wiring layer 24 is formed on the lower surface side of the insulating layer 21. The lower wiring layer 24 may be formed by any method, and may be formed, for example, in the same manner as the above-mentioned upper wiring layer forming step S2. The lower wiring layer 24 thus formed is electrically connected to the upper wiring layer 25 via the through-wires 221 .

[0180] [5] Solder bump formation process S5 6(l), solder bumps 26 are formed on the lower wiring layer 24. In addition, a protective film such as a solder resist layer may be formed on the upper wiring layer 25 and the lower wiring layer 24 as necessary. In this manner, the through electrode substrate 2 is obtained.

[0181] The through electrode substrate 2 shown in Fig. 6(l) can be divided into a plurality of regions. Therefore, for example, by dividing the through electrode substrate 2 along the dashed line shown in Fig. 6(l), a plurality of through electrode substrates 2 can be efficiently manufactured. For example, a diamond cutter or the like can be used for dividing the substrate.

[0182] [6]Lamination process S6 Next, a semiconductor package 3 is placed on each individual through hole electrode substrate 2. In this way, the electronic device 1 shown in FIG.

[0183] Such a manufacturing method for the electronic device 1 can be applied to a wafer level process or a panel level process using a large-area substrate, thereby improving the manufacturing efficiency of the electronic device 1 and reducing costs.

[0184] <Optical devices> The optical device of this embodiment includes: A light-emitting element; Wiring electrically connected to the light-emitting element; an insulating film covering the wiring; Equipped with The insulating film is a cured film of the above-mentioned photosensitive resin composition.

[0185] Examples of optical devices include display devices such as liquid crystal displays, organic EL displays, touch panels, electronic paper, color filters, mini LED displays, and micro LED displays; light-emitting devices such as LEDs, mini LEDs, micro LEDs, and laser diodes; and light-receiving devices such as solar cells and CMOS. The photosensitive resin composition of the present embodiment can be used for rewiring layers, interlayer insulating films, sealing materials (top coats), etc. The photosensitive resin composition of the present embodiment can be particularly suitably used for micro LEDs.

[0186] The method for producing an optical device according to this embodiment and the structure of an optical device including a cured product of the photosensitive resin composition according to this embodiment will be described in more detail below with reference to the drawings.

[0187] (Film Forming Step: FIG. 7A) In the film forming step, a photosensitive resin film 73 is formed on the surface of a substrate 71 having a step 710 by using the photosensitive resin composition of this embodiment. There is no particular limitation on the substrate 71. Examples of the substrate 71 include a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, and a GaN wafer. The step 710 is, for example, a Cu rewiring. Of course, the step 710 may be a step other than a Cu rewiring. The height of the step 710 is, for example, 1 to 10 μm, and preferably 1 to 5 μm. The thickness of the photosensitive resin film 73 (the thickness of the portion without the step 710) is, for example, 1 to 15 μm, and preferably 1 to 10 μm.

[0188] Examples of a method for forming the photosensitive resin film 73 include a method for providing a liquid photosensitive resin composition on a substrate by a spin coating method, a spray coating method, a dipping method, a printing method, a roll coating method, an inkjet method, etc. A typical method for forming the resin film is spin coating. The thickness of the photosensitive resin film 73 can be adjusted by changing the film formation conditions or adjusting the viscosity of the photosensitive resin composition.

[0189] After the film-forming step and before the exposure step, it is preferable to heat-dry the photosensitive resin film 73. This heat-drying is sometimes called "pre-bake". The temperature for drying by heating is usually 50 to 180° C., preferably 60 to 150° C. The time for drying by heating is usually 30 to 600 seconds, preferably about 30 to 300 seconds. This drying by heating can sufficiently remove the solvent in the photosensitive resin composition. Heating is typically performed using a hot plate, an oven, or the like.

[0190] (Exposure process: Figure 7B) In the exposure step, the photosensitive resin film 73 is exposed through a photomask 720. Examples of active light for exposure include X-rays, electron beams, ultraviolet rays, and visible light. In terms of wavelength, active light having a wavelength of 200 to 500 nm is preferred. In terms of pattern resolution and ease of handling of the device, the light source is preferably g-rays, h-rays, or i-rays from a mercury lamp. Two or more types of light may be mixed and used. The exposure device is preferably a contact aligner, a mirror projection or a stepper. The exposure dose in the exposure process is usually 40 to 1500 mJ / cm 2 , preferably 80 to 1000 mJ / cm 2 It is appropriately adjusted between these values ​​depending on the sensitivity of the photosensitive resin composition, the thickness of the resin film, the shape of the pattern to be obtained, and the like.

[0191] It is preferable to heat the resin film (post-exposure baking) between the exposure step and the development step. This allows the reaction of substances (photosensitizers, etc.) that have been cleaved or decomposed by exposure to proceed, and is expected to improve the pattern shape, etc. The temperature and time of the post-exposure baking are, for example, 50 to 200°C and about 10 to 600 seconds.

[0192] (Developing process: Figure 7C) In the development process, the photosensitive resin film exposed in the exposure process is developed using a developer. As a result, a part of the photosensitive resin film 73 is removed to obtain a resin film 73A having an opening 75. The photosensitive resin composition of this embodiment is generally negative type. Therefore, the opening 75 is provided in a portion corresponding to the light-shielding portion of the photomask 720. The development step can be carried out by, for example, an immersion method, a paddle method, a rotary spray method, or the like.

[0193] In this embodiment, the developer preferably contains an organic solvent. More specifically, the developer is preferably a developer mainly composed of an organic solvent (a developer in which 95% by mass or more of the components are organic solvents). By developing with a developer containing an organic solvent, it becomes possible to suppress swelling of the pattern caused by the developer, as compared to the case of developing with an alkaline developer (water-based). In other words, it is easier to obtain a finer pattern.

[0194] Specific examples of organic solvents that can be used in the developer include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether-based solvents such as propylene glycol monomethyl ether. As the developer, an organic solvent developer may be used that is made of only an organic solvent and does not contain any impurities other than those that are inevitably contained. Although the inevitably contained impurities include metal elements, from the viewpoint of preventing contamination of electronic devices, it is better to have as few inevitably contained impurities as possible.

[0195] The time for the development step is usually within the range of about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the thickness of the resin film, the shape of the pattern to be formed, and the like.

[0196] Between the developing step and the subsequent step, for example, a curing step for curing the resin film 73A may be performed. The curing can be performed, for example, by a heat treatment at 150 to 250° C. for 30 to 240 minutes. By forming the resin film 73A using the photosensitive resin composition of this embodiment, the surface (upper surface) of the resin film 73A has good flatness even after such a curing step.

[0197] (Additional rewiring process: Figure 7D) A Cu rewiring 711 different from the step 710 (for example, a Cu rewiring) can be provided in the portion of the opening 75 provided in the development process. At this time, since the upper surface of the resin film 73A has high flatness, the fine Cu rewiring 711 can be provided with high precision.

[0198] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0199] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It should be noted that the present invention is not limited to the Examples. In the following, "TEMPO" is an abbreviation for "2,2,6,6-tetramethylpiperidine-1-oxyl." Other abbreviations will be explained appropriately in the text.

[0200] <Synthesis of polyimide resin> (Synthesis of polyimide resin (A-1)) In a 5L separable flask equipped with a stirrer and a cooling tube, 304.2g (0.95 mol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB), 355.39g (0.80 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 62.04g (0.20 mol) of 4,4'-oxydiphthalic dianhydride, and 1684g of GBL were added and reacted at room temperature for 16 hours under a nitrogen atmosphere to carry out a polymerization reaction. The temperature of the reaction solution was then raised to 180°C in an oil bath and reacted for 3 hours, after which it was cooled to room temperature to produce a polyimide resin solution. The reaction solution was then added dropwise to a mixed solution of isopropanol / water = 4 / 7 while stirring to precipitate a resin solid. The solid obtained was roughly filtered and then washed with isopropanol / water = 4 / 7 to obtain a white solid polyimide. The white solid obtained was vacuum dried at 200 ° C to obtain a polyimide resin (A-1) having an acid anhydride group at the end. The weight average molecular weight (Mw) of the polyimide resin (A-1) measured by GPC was 49,000. The imidization rate of the polyimide resin (A-1) measured by NMR was 98%.

[0201] [ka]

[0202] (Synthesis of polyimide resin (A-2)) In a 5L separable flask equipped with a stirrer and a cooling tube, 268.3g (0.95 mol) of 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (MED-J), 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate (TMPBP-TME) 494.87g (0.8 mol), 62.04g (0.20 mol) of 4,4'-oxydiphthalic dianhydride and 1684g of GBL were added and reacted at room temperature for 16 hours under a nitrogen atmosphere to carry out polymerization reaction. The temperature of the reaction solution was then raised to 180°C in an oil bath and reacted for 3 hours, after which it was cooled to room temperature to prepare a polyimide resin solution. The reaction solution was then added dropwise to a mixed solution of isopropanol / water = 4 / 7 while stirring to precipitate a resin solid. The solid obtained was roughly filtered and then washed with isopropanol / water = 4 / 7 to obtain a white solid polyimide. The white solid obtained was vacuum dried at 200 ° C to obtain a polyimide resin (A-2) having an acid anhydride group at the end. The weight average molecular weight (Mw) of the polyimide resin (A-2) measured by GPC was 49000. The imidization rate of the polyimide resin (A-2) measured by NMR was 98%.

[0203] [ka]

[0204] (Synthesis of polyimide resin (A-3)) In a 5L separable flask equipped with a stirrer and a cooling tube, 304.22g (0.95 mol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB), 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate (TMPBP-TME) 494.87g (0.8 mol), 62.04g (0.20 mol) of 4,4'-oxydiphthalic dianhydride and 1684g of GBL were added and reacted at room temperature for 16 hours under a nitrogen atmosphere to carry out polymerization reaction. The temperature of the reaction solution was then raised to 180°C in an oil bath and reacted for 3 hours, after which it was cooled to room temperature to prepare a polyimide resin solution. The reaction solution was then added dropwise to a mixed solution of isopropanol / water = 4 / 7 while stirring to precipitate a resin solid. The solid obtained was roughly filtered and then washed with isopropanol / water = 4 / 7 to obtain a white solid polyimide. The white solid obtained was vacuum dried at 200 ° C to obtain a polyimide resin (A-3) having an acid anhydride group at the end. The weight average molecular weight (Mw) of the polyimide resin (A-3) measured by GPC was 49000. The imidization rate of the polyimide resin (A-3) measured by NMR was 98%.

[0205] [ka]

[0206] (Synthesis of polyimide resin (A-4)) In a 5L separable flask equipped with a stirrer and a cooling tube, 304.22g (0.95 mol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB), 355.89g (0.8 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 62.04g (0.20 mol) of 4,4'-oxydiphthalic dianhydride, and 1684g of GBL were added and reacted at room temperature for 16 hours under a nitrogen atmosphere to carry out a polymerization reaction. The temperature of the reaction solution was then raised to 180°C in an oil bath and reacted for 3 hours, after which it was cooled to room temperature to produce a polyimide resin solution. The reaction solution was then added dropwise to a mixed solution of isopropanol / water = 4 / 7 while stirring to precipitate a resin solid. The solid obtained was roughly filtered and then washed with isopropanol / water = 4 / 7 to obtain a white solid polyimide. The white solid obtained was vacuum dried at 200 ° C to obtain a polyimide resin (A-4) having an acid anhydride group at the end. The weight average molecular weight (Mw) of the polyimide resin (A-4) measured by GPC was 49000. The imidization rate of the polyimide resin (A-4) measured by NMR was 98%.

[0207] [ka]

[0208] <Preparation of Photosensitive Resin Composition> The raw materials were mixed according to Table 1 below and stirred at room temperature until the raw materials were completely dissolved to obtain a solution. The solution was then filtered through a nylon filter with a pore size of 0.2 μm. In this way, a varnish-like photosensitive resin composition was obtained.

[0209] Details of the raw materials for each component in Table 1 are as follows:

[0210] <(A) Polyimide resin> (A-1) Polyimide resin (A-1) synthesized above (A-2) Polyimide resin (A-2) synthesized above (A-3) Polyimide resin (A-3) synthesized above (A-4) Polyimide resin (A-4) synthesized above

[0211] <(B) Polyfunctional (meth)acrylate compound> (B-1) Viscoat #195 (Osaka Organic Industry Co., Ltd., 1,4-butanediol diacrylate) (B-2) Viscoat #802 (Osaka Organic Industry Co., Ltd., a mixture of compounds having 5 to 10 acryloyl groups) (B-3) A-9550 (manufactured by Shin-Nakamura Chemical Co., Ltd., a mixture of compounds having 5 to 6 acryloyl groups) (B-4) Viscoat #300 (Osaka Organic Industry Co., Ltd., a mixture of compounds having 3 to 4 acryloyl groups)

[0212] The structures of the above (B-1) to (B-4) are shown below.

[0213] [ka]

[0214] <(C) Photosensitizer> (C-1) Irugacure OXE01 (BASF, oxime ester type photoradical generator)

[0215] <(E) Thermal radical generator> (E-1) Perkadox BC (manufactured by Nouryon Chemical Co., Ltd., organic peroxide, dicumyl peroxide)

[0216] <(F) Crosslinking agent> (F-1) 4HBAGE (4-hydroxybutyl acrylate glycidyl ether, compound of chemical formula (2), manufactured by Mitsubishi Chemical Corporation) (F-2) CYCLOMER M100 (manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl methacrylate, compound of chemical formula (3))

[0217] <(G) Silane coupling agent> (G-1) X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.) (G-2) KBM-403 (Shin-Etsu Chemical Co., Ltd.)

[0218] <(H) Curing catalyst> (H-1) Tetraphenylphosphonium 4,4'-sulfonyldiphenolate The curing catalyst (H-1) can be synthesized as follows. In a separable flask equipped with a stirrer, 37.5g (0.15mol) of 4,4'-bisphenol S and 100mL of methanol were charged, stirred and dissolved at room temperature, and a solution of 4.0g (0.1mol) of sodium hydroxide dissolved in 50mL of methanol was added while stirring. Next, a solution of 41.9g (0.1mol) of tetraphenylphosphonium bromide dissolved in 150mL of methanol was added. Stirring was continued for a while, and after adding 300mL of methanol, the solution in the flask was dropped into a large amount of water while stirring, and a white precipitate was obtained. The precipitate was filtered and dried. As a result, a white crystalline curing catalyst (H-1) was obtained.

[0219] <(I) Surfactant> (I-1) FC4432 (3M, fluorine-based)

[0220] <(J)(Solvent)> (J-1) γ-butyrolactone (GBL) (J-2) Ethyl lactate (EL)

[0221] <(D) Polymerization inhibitor> (D-1) Irganox 1035 (BASF, hindered phenol compound) (D-2) Irganox 1010 (BASF, hindered phenol compound) (D-3) 4-benzoyloxy TEMPO (Seiko Chemical Co., Ltd., N-oxyl compound) (D-4) 2,6-di-tert-butyl-p-cresol (Tokyo Chemical Industry Co., Ltd., hindered phenol compound) (D-5) N,N-diphenylnitrosamide (Tokyo Chemical Industry Co., Ltd., N-oxyl compound) (D-6) Capferon (Tokyo Chemical Industry Co., Ltd., N-oxyl compound) (D-7) TEMPO (Tokyo Chemical Industry Co., Ltd., N-oxyl compound) (D-8) 4-HydroxyTEMPO (Seiko Chemical Co., Ltd., N-oxyl compound) (D-9) Sebacic acid BisTEMPO (Seiko Chemical Co., Ltd., N-oxyl compound) (D-10) Irganox 1726 (BASF, hindered phenol compound) (D-11) Irganox 1520L (BASF, hindered phenol compound)

[0222] The structures of the above (D-1) to (D-11) are shown below.

[0223] [ka]

[0224] <Evaluation of focus margin> The photosensitive resin composition of each Example and Comparative Example was applied to a 12-inch plated copper (Ra=0.08 μm) wafer using a spin coater so that the film thickness after drying was 5 μm. Then, the composition was dried on a hot plate at 120° C. for 3 minutes to obtain a photosensitive resin film. This photosensitive resin film was irradiated with i-line through a photomask (on which a 3 μmφ round via hole pattern was drawn) using an i-line stepper (Canon Corporation, FPA-5500iX, NA=0.28) while changing the exposure dose from 190 mJ to 550 mJ at a rate of 30 mJ / min and the focus from -9 μm to +3 μm at a rate of 1 μm. Then, the film was developed at 2500 rpm for 30 seconds using cyclopentanone as a developer, rinsed at 2500 rpm for 10 seconds using PGMEA, and dried by spinning for 20 seconds to obtain a developed film (negative pattern). Then, the film was dried at 170°C for 10 minutes on a hot plate, and then heat-treated at 200°C for 120 minutes in a nitrogen atmosphere. As a result, a cured product of the photosensitive resin composition was obtained. Within the above-mentioned range of exposure dose, for those in which a 3 μmΦ via hole was opened without foot or bridge, the difference between the maximum and minimum focus values ​​was calculated as the focus margin, and the results are shown in Table 1. In each of the examples and comparative examples, when the focus margin could be calculated at multiple exposure doses, the largest focus margin value was shown.

[0225] <Evaluation of tensile elongation> (Preparation of test pieces for measuring tensile elongation) The photosensitive resin composition was spin-coated onto an 8-inch silicon wafer so that the film thickness after drying would be 10 μm, and then heated at 120° C. for 3 minutes to obtain a photosensitive resin film. The resulting photosensitive resin film was exposed to 300 mJ / cm irradiated with a high-pressure mercury lamp. 2 After that, the exposed resin film was immersed in cyclopentanone together with the silicon wafer for 30 seconds. After that, the resin film was heat-treated at 200° C. for 120 minutes in a nitrogen atmosphere. As a result, a cured product of the photosensitive resin composition was obtained. The obtained cured product was cut together with the silicon wafer into a width of 5 mm using a dicing saw, and then peeled off from the substrate by immersing in a 2% by mass aqueous solution of hydrofluoric acid. The peeled film was dried at 60°C for 10 hours to obtain a test piece (30 mm x 5 mm x 10 μm thick).

[0226] (Measurement of Tensile Elongation) A tensile test was carried out on the obtained test piece using a tensile tester (Tensilon RTC-1210A manufactured by Orientec Co., Ltd.) in an atmosphere of 23°C according to a method conforming to JIS K 7161, and the tensile elongation of the test piece was measured. The elongation speed in the tensile test was 5 mm / min. The unit of the tensile elongation is %.

[0227] The composition of the raw materials for each composition and the above evaluation results are shown in Table 1.

[0228] [Table 1] [Table 2]

[0229] As shown in Table 1, the photosensitive resin compositions of Examples 1 to 32 had good elongation properties and also had large focus margins.

[0230] This application claims priority based on Japanese Patent Application No. 2021-161640, filed on September 30, 2021, the disclosure of which is incorporated herein in its entirety. [Explanation of symbols]

[0231] 1. Electronic Devices 1A Electronic Device 1B Electronic Devices 2 Through-hole electrode substrate 3. Semiconductor Package 5. Photosensitive resin varnish 21 Insulating layer 23 Semiconductor Chips 24 Lower wiring layer 24A lower wiring layer 24B Lower wiring layer 25 Upper wiring layer 26 Solder Bumps 27 Chip embedding structure 31 Package substrate 32 Semiconductor Chips 33 Bonding Wire 34 Sealing layer 35 Solder Bumps 202 Substrate 221 Through Wiring 222 Through Wiring 231 rand 240 Organic Insulating Layer 241 Organic Insulating Layer 242 Organic Insulating Layer 243 Wiring layer 245 Bump Adhesion Layer 251 Organic Insulating Layer 252 Organic Insulating Layer 253 Wiring layer 254 Through Wiring 412 Mask 423 Opening 424 Opening 2510 Photosensitive resin layer 2520 Photosensitive resin layer 71 Substrate 73 Photosensitive resin film 73A Resin membrane 75 Aperture 710 Step 711 Cu rewiring 720 Photomask S1 Chip placement process S2 Upper wiring layer formation process S20 First resin film placement process S21 First exposure process S22 1st development process S23 1st curing process S24 Wiring layer formation process S25 Second resin film placement process S26 Second exposure process S27 2nd development process S28 2nd curing process S29 Through-hole wiring formation process S3 Substrate peeling process S4 Lower wiring layer formation process S5 Solder bump formation process S6 Lamination process W diameter

Claims

1. A polyimide resin (A), a polyfunctional (meth)acrylate compound (B); a photosensitizer (C); a polymerization inhibitor (D); A photosensitive resin composition comprising: The polyimide resin (A) contains a structure represented by the following general formula (a): 【Chemical 1】 In general formula (a), X is a divalent organic group; Y is a tetravalent organic group; the polymerization inhibitor (D) contains one or more compounds selected from the group consisting of hindered phenol compounds and N-oxyl compounds; Photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, The number of moles of imide groups contained in the polyimide resin (A) is represented by IM, When the number of moles of amide groups contained in the polyimide resin (A) is AM, A photosensitive resin composition having an imidization rate, expressed as {IM / (IM+AM)}×100(%), of 90% or more.

3. The photosensitive resin composition according to claim 1, The photosensitive resin composition includes a polyimide resin (A) containing a fluorine atom.

4. The photosensitive resin composition according to claim 1, The photosensitive resin composition, wherein the polyfunctional (meth)acrylate compound (B) contains a trifunctional to tetrafunctional (meth)acrylate compound (B1).

5. The photosensitive resin composition according to claim 1, The photosensitive resin composition, wherein the polyfunctional (meth)acrylate compound (B) contains a pentafunctional or higher (meth)acrylate compound (B2).

6. The photosensitive resin composition according to claim 1, the content of the polyfunctional (meth)acrylate compound (B) relative to 100 parts by mass of the polyimide resin (A) is 25 parts by mass or more and 100 parts by mass or less.

7. The photosensitive resin composition according to claim 1, The photosensitive resin composition, wherein the photosensitizer (C) contains a photoradical generator.

8. The photosensitive resin composition according to claim 7, The photosensitive resin composition, wherein the photoradical generator comprises an oxime ester-based photoradical generator.

9. The photosensitive resin composition according to claim 1, a photosensitive resin composition in which the content of the photosensitizer (C) relative to 100 parts by mass of the polyimide resin (A) is 5 parts by mass or more and 30 parts by mass or less.

10. The photosensitive resin composition according to claim 1, the content of the polymerization inhibitor (D) relative to 100 parts by mass of the polyimide resin (A) is 0.1 parts by mass or more and 5 parts by mass or less.

11. The photosensitive resin composition according to claim 1, a content of the polymerization inhibitor (D) relative to 100 parts by mass of the photosensitizer (C) being 1 part by mass or more and 30 parts by mass or less;

12. The photosensitive resin composition according to claim 1, The photosensitive resin composition further comprises a thermal radical generator (E).

13. The photosensitive resin composition according to claim 1, The photosensitive resin composition further comprises a crosslinking agent (F).

14. The photosensitive resin composition according to claim 13, The photosensitive resin composition, wherein the crosslinking agent (F) contains a compound having an epoxy-containing group at one end of the molecule and a (meth)acryloyl group at the other end.

15. The photosensitive resin composition according to claim 1, The photosensitive resin composition further comprises a silane coupling agent (G).

16. The photosensitive resin composition according to claim 1, A photosensitive resin composition used to form insulating layers in electronic devices.

17. The photosensitive resin composition according to claim 1, A photosensitive resin composition used to form an insulating layer in an optical device.

18. a film-forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 1 to 16; an exposure step of exposing the photosensitive resin film to light; a developing step of developing the exposed photosensitive resin film; A method for manufacturing an electronic device, comprising:

19. 20. The method of manufacturing an electronic device according to claim 18, comprising: The method for manufacturing an electronic device further comprises, after the developing step, a thermal curing step of heating and curing the exposed photosensitive resin film.

20. An electronic device comprising a cured film of the photosensitive resin composition according to any one of claims 1 to 16.

21. A light-emitting element; Wiring electrically connected to the light-emitting element; an insulating film covering the wiring; Equipped with An optical device, wherein the insulating film is a cured film of the photosensitive resin composition according to any one of claims 1 to 15 and 17.

22. 22. The optical device of claim 21, wherein the light emitting element is a micro LED.

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