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

Abstract

To provide a photosensitive resin composition capable of manufacturing a highly reliable electronic device by heating and curing the composition at approximately 170°C to form a cured film.SOLUTION: There is provided a photosensitive resin composition which comprises a polyamide resin and / or a polyimide resin, wherein a cured film obtained by heating the photosensitive resin composition at 170°C for 2 hours has a storage elastic modulus E'220 at 220°C of 0.5 to 3.0 GPa by measuring dynamic viscoelasticity under the following conditions. [Conditions] Frequency: 1 Hz, Temperature: 30 to 300°C, Temperature rising rate: 5°C / min, Measurement mode: Tensile mode.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing an electronic device, and an electronic device. More specifically, the present invention relates to a photosensitive resin composition containing a polyamide resin and / or a polyimide resin, a method for producing an electronic device using the photosensitive resin composition, and an electronic device that can be produced by the method for producing an electronic 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 investigated.

[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] As electronic devices become more advanced and complex, they are being required to be more reliable than ever before. Therefore, there is a demand to improve the reliability of electronic devices by improving the cured film (improving the photosensitive resin composition used to form the cured film). Furthermore, in recent years, there has been a demand to lower the heating temperature when forming a cured film (for example, to about 170° C.) in order to reduce thermal damage to semiconductor chips.

[0007] The present invention has been made in view of the above circumstances. One of the objects of the present invention is to provide a photosensitive resin composition that can be cured by heating at about 170° C. to form a cured film, thereby enabling the production of highly reliable electronic devices. [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, there is provided the following photosensitive resin composition. A photosensitive resin composition containing a polyamide resin and / or a polyimide resin, The photosensitive resin composition was heated at 170°C for 2 hours to obtain a cured film, and the dynamic viscoelasticity was measured under the following conditions. The storage modulus E' at 220°C was 220 The photosensitive resin composition has a compressive strength of 0.5 to 3.0 GPa. [conditions] Frequency: 1Hz Temperature: 30~300℃ Heating rate: 5℃ / min Measurement mode: Tensile mode

[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, comprising: is provided.

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

[0012] The photosensitive resin composition of the present invention can be cured by heating at about 170° C. to form a cured film, thereby enabling the production of highly reliable electronic devices. [Brief description of the drawings]

[0013] [Figure 1] 1A to 1C are diagrams for explaining a method for manufacturing an electronic device. [Diagram 2] 1A to 1C are diagrams for explaining a method for manufacturing an electronic device. [Diagram 3] 1A to 1C are diagrams for explaining a method for manufacturing an electronic device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] 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 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 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.

[0015] 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".

[0016] 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 encompass 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.

[0017] <Photosensitive resin composition> The photosensitive resin composition of the present embodiment contains a polyamide resin and / or a polyimide resin. The photosensitive resin composition of the present embodiment was heated at 170° C. for 2 hours to obtain a cured film, and the dynamic viscoelasticity was measured under the following conditions. The storage modulus E′ at 220° C. was 220 is 0.5 to 3.0 GPa. [conditions] Frequency: 1Hz Temperature: 30~300℃ Heating rate: 5℃ / min Measurement mode: Tensile mode

[0018] In the electronic device manufacturing process, various types of "heating" are performed, and the cured film may reach high temperatures. The present inventors have hypothesized that high temperatures caused by heating may adversely affect the cured film in the electronic device, resulting in a decrease in the reliability of the electronic device. More specifically, the cured film may be altered / softened at high temperatures, which may reduce the adhesive strength between the cured film and the substrate, resulting in peeling of the cured film, resulting in a decrease in the reliability of the electronic device.

[0019] Based on this idea, the present inventors thought that if it were possible to design a photosensitive resin composition capable of forming a cured film that is not easily softened at 220°C (having a relatively large elastic modulus at ≒220°C), which is a heating temperature that can be used in heating such as a reflow process, then the decrease in adhesion of the cured film due to heating could be suppressed, and as a result, the reliability of electronic devices could be improved. Furthermore, they thought that if such a cured film could be formed by heating at about 170°C, it would be possible to follow the recent trend in electronic device manufacturing.

[0020] Taking this idea a step further, the present inventors have determined that in a photosensitive resin composition containing a polyamide resin and / or a polyimide resin, (i) the storage modulus E' of the cured film at 220°C is an index of the resistance of the cured film to softening at 220°C. 220 (ii) adopting that E' 220 In this study, we designed a new photosensitive resin composition with a hardness of 0.5 GPa or more. The conditions for forming the cured film were set to "170°C for 2 hours," in line with the recent trend in electronic device manufacturing. By applying this new photosensitive resin composition to the manufacture of electronic devices (for example, the formation of an insulating layer in an electronic device), the present inventors have succeeded in improving the reliability of the electronic devices.

[0021] By the way, in principle, E' 220It is considered that the larger the better, but from the viewpoint of cost and practical composition design, in this embodiment, E' 220 The upper limit is set at 3.0 GPa. E' 220 The pressure may be 0.5 to 3.0 GPa, preferably 0.6 to 2.5 GPa, and more preferably 0.7 to 2.0 GPa.

[0022] In this embodiment, E' 220 A photosensitive resin composition having a modulus of 0.5 GPa or more and 3.0 GPa or less can be produced by appropriately selecting the materials, their blending, preparation method, etc. Preferred materials for the photosensitive resin composition of the present embodiment will be described below, and examples thereof include the selection of an appropriate polyfunctional (meth)acrylate as a component to be used in combination with a polyamide resin and / or a polyimide resin.

[0023] The photosensitive resin composition of this embodiment will be further described.

[0024] (Polyamide resin and / or polyimide resin) The photosensitive resin composition of the present embodiment contains a polyamide resin and / or a polyimide resin. 220 As long as the compressive strength is 0.5 to 3.0 GPa, the structure, molecular weight, amount used, etc. of the polyamide resin and / or polyimide resin are not limited.

[0025] From the viewpoint of reducing the amount of shrinkage during curing, the photosensitive resin composition of the present embodiment preferably contains a polyimide resin, and more preferably contains a polyimide resin having an imide ring structure. When the number of moles of imide groups contained in the polyimide resin is IM and the number of moles of amide groups contained in the polyimide resin 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 short, it is preferable that the polyimide resin is a resin that has no or few ring-open amide structures and many ring-closed imide structures. By using such a polyimide resin, shrinkage due to heating (curing shrinkage) can be further suppressed (because dehydration due to ring-closing reaction does not occur). This can further improve the reliability of electronic devices and the flatness of cured films. 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.

[0026] The polyamide resin and / or polyimide resin preferably contains fluorine atoms. As the inventors have found, polyamide resins and / or polyimide resins containing fluorine atoms tend to have better organic solvent solubility than those not containing fluorine atoms. Therefore, by using polyamide resins and / or polyimide resins containing fluorine atoms, the photosensitive resin composition is easily in the form of a varnish. The amount (mass ratio) of fluorine atoms in the fluorine-containing polyamide resin and / or polyimide resin is, for example, 1 to 30 mass%, preferably 3 to 28 mass%, more preferably 5 to 25 mass%. By containing a relatively large amount of fluorine atoms in the resin, sufficient solubility in organic solvents 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.

[0027] By designing the ends of the polyamide resin and / or polyimide resin in various ways, for example, the mechanical properties (such as tensile elongation) of the cured product can be further improved.

[0028] For example, the polyamide resin and / or polyimide resin 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.

[0029] Preferably, the polyamide resin and / or polyimide resin has an acid anhydride group at its terminal. In the photosensitive resin composition of this embodiment, the acid anhydride group and the epoxy group can 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.

[0030] Regarding the terminal structure, it is preferable that the polyamide resin and / or polyimide resin does not have a maleimide structure at its terminal.

[0031] The polyamide resin preferably contains a structural unit represented by the following general formula (PA-1).

[0032] [ka]

[0033] The polyimide resin preferably contains a structural unit represented by the following general formula (PI-1).

[0034] [ka]

[0035] In general formulas (PA-1) and (PI-1), X is a divalent organic group; Y is a tetravalent organic group.

[0036] In the general formulae (PA-1) and (PI-1), at least one of X and Y is preferably a fluorine atom-containing group. From the viewpoint of solubility in organic solvents, it is preferred that both X and Y in the general formulae (PA-1) and (PI-1) are fluorine atom-containing groups.

[0037] In the general formulas (PA-1) and (PI-1), 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. This tends to further increase heat resistance. The benzene ring here may be substituted with a fluorine atom, a fluorinated alkyl group (preferably a trifluoromethyl group) or other fluorine atom-containing group, or may be substituted with other groups. In the general formulae (PA-1) and (PI-1), 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. In the general formulae (PA-1) and (PI-1), the divalent organic group for X has 6 to 30 carbon atoms, for example. In the general formulae (PA-1) and (PI-1), the tetravalent organic group for Y has 6 to 20 carbon atoms, for example. Each of the two imide rings in general formula (PI-1) is preferably a five-membered ring.

[0038] The polyamide resin more preferably contains a structural unit represented by the following general formula (PA-2).

[0039] [ka]

[0040] The polyimide resin more preferably contains a structural unit represented by the following general formula (PI-2).

[0041] [ka]

[0042] In general formulas (PA-2) and (PI-2), X has the same meaning as X in formulae (PA-1) and (PI-1). Y' represents a single bond or an alkylene group.

[0043] Specific embodiments of X are the same as those explained in formulae (PA-1) and (PI-1). 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.

[0044] Typically, polyamide resins can be obtained by reacting (condensation polymerization) diamines with acid dianhydrides. Polyimide resins can be obtained by imidizing (ring-closing) polyamide resins. In addition, a desired functional group may be introduced into the polymer terminal as necessary. For specific reaction conditions, the examples below and the description of Patent Document 1 above can be referred to.

[0045] In the final polyamide resin and / or polyimide resin, the diamine is incorporated into the polymer as a divalent organic group X in the general formula (PA-1) or (PI-1), and the acid dianhydride is incorporated into the polymer as a tetravalent organic group Y in the general formula (PA-1) or (PI-1). In the synthesis of the polyamide and / or polyimide resins, one or more diamines may be used, and one or more dianhydrides may be used.

[0046] 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

[0047] 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.

[0048] The ratio of diamine and acid dianhydride used is basically 1:1 in molar ratio. However, in order to obtain a desired terminal structure, one may be used in excess. Specifically, by using an excess of diamine, the terminals (both terminals) of the polyamide resin and / or polyimide resin tend to become amino groups. On the other hand, by using an excess of acid dianhydride, the terminals (both terminals) of the polyamide resin and / or polyimide resin tend to become acid anhydride groups. As described above, in this embodiment, it is preferable that the polyamide resin and / or polyimide resin have acid anhydride groups at their terminals. Therefore, in this embodiment, it is preferable to use an excess of acid dianhydride when synthesizing the polyamide resin and / or polyimide resin.

[0049] The amino group and / or acid anhydride group at the end of the polyamide resin and / or polyimide resin obtained by condensation polymerization may be reacted with a certain reagent so that the resin end has a desired functional group.

[0050] The weight average molecular weight of the polyamide resin and / or polyimide resin 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 polyamide resin and / or polyimide resin is relatively large, for example, the cured film can have sufficient heat resistance. In addition, when the weight average molecular weight of the polyamide resin and / or polyimide resin is not too large, the polyamide resin and / or polyimide resin 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.

[0051] (Polyfunctional (meth)acrylate compound) The photosensitive resin composition of the present embodiment preferably contains a polyfunctional (meth)acrylate compound. The polyfunctional (meth)acrylate compound may be, without particular limitation, a compound having two or more (meth)acryloyl groups in one molecule.

[0052] According to the findings of the present inventors, by using a polyamide resin and / or a polyimide resin in combination with a polyfunctional (meth)acrylate compound, it is possible to obtain a high-performance liquid crystal composition having a high molecular weight. 220 It is easy to design a photosensitive resin composition having a compressive strength of 0.5 to 3.0 GPa, and the performance of the cured film tends to be improved.

[0053] Although the details are unclear, it is believed that when the polyfunctional (meth)acrylate compound cures (polymerizes), a structure is formed in which it is intricately "entangled" with the polyamide resin and / or polyimide resin. In particular, it is speculated that the polyfunctional (meth)acrylate compound forms a network structure that "wraps" the cyclic skeleton of a polyimide resin having a cyclic skeleton such as an imide ring, or a polyamide resin that may have a cyclic skeleton due to at least a portion of the polyamide structure being closed by heat. The formation of such a complexly entangled structure results in E' 220 It is estimated that the compressive strength will be 0.5 to 3.0 GPa, and the performance of the cured film will improve.

[0054] From the viewpoint of realizing the above-mentioned entangled structure and from the viewpoint of obtaining a cured film having high durability and good chemical resistance, the polyfunctional (meth)acrylate compound is preferably 3 or more functional. There is no particular upper limit to the number of functional groups of the polyfunctional (meth)acrylate compound, but from the viewpoint of ease of obtaining raw materials, the upper limit of the number of functional groups is, for example, 11 functional groups. Generally speaking, when a polyfunctional (meth)acrylate compound 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 having a small number of functional groups ((meth)acryloyl groups) is used, the mechanical properties of the cured film, such as tensile elongation, tend to be good.

[0055] As an example, the polyfunctional (meth)acrylate compound preferably contains a seven or more functional (meth)acrylate compound.

[0056] As an example, the polyfunctional (meth)acrylate compound preferably contains a penta- or hexafunctional (meth)acrylate compound.

[0057] As an example, the polyfunctional (meth)acrylate compound preferably contains a tri- or tetrafunctional (meth)acrylate compound.

[0058] As an example, the polyfunctional (meth)acrylate compound may include a compound represented by the following general formula: 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. Multiple R's may be the same or different.

[0059] [ka]

[0060] Specific examples of the polyfunctional (meth)acrylate compound include the following: Of course, the polyfunctional (meth)acrylate compound is not limited to these.

[0061] 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.

[0062] 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.).

[0063] When the photosensitive resin composition contains a multifunctional (meth)acrylate compound, it may contain only one multifunctional (meth)acrylate compound, or may contain two or more multifunctional (meth)acrylate compounds. In the latter case, it is preferable to use multifunctional (meth)acrylate compounds having different numbers of functional groups in combination. It is believed that by using multifunctional (meth)acrylate compounds having different numbers of functional groups in combination, a more complex "entangled structure" is formed, and the properties of the cured film are further improved. Incidentally, some commercially available polyfunctional (meth)acrylate compounds are mixtures of (meth)acrylates having different numbers of functional groups.

[0064] When a polyfunctional (meth)acrylate compound is used, the amount of the polyfunctional (meth)acrylate compound per 100 parts by mass of the polyamide resin and / or polyimide resin is preferably 50 to 200 parts by mass, more preferably 60 to 150 parts by mass. The amount of the polyfunctional (meth)acrylate compound 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 the present embodiment, it is considered that an "entanglement structure" between the polyamide resin and / or polyimide resin and the polyfunctional (meth)acrylate is formed by curing, and by appropriately adjusting the amount of the polyfunctional (meth)acrylate compound used relative to the polyamide resin and / or polyimide resin, the polyamide resin and / or polyimide resin and the polyfunctional (meth)acrylate compound are appropriately entangled, and the amount of excess components not involved in the entanglement is reduced. It is considered that the performance is further improved.

[0065] (Photosensitizer) The photosensitive resin composition of the present embodiment preferably contains a photosensitizer. The photosensitizer is not particularly limited as long as it is capable of generating active species by light to cure the photosensitive resin composition.

[0066] The photosensitizer preferably contains a photoradical generator, which is particularly effective in polymerizing a polyfunctional (meth)acrylate compound.

[0067] 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, Examples of suitable compounds include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. Of these, oxime ester compounds can be particularly preferably used.

[0068] When the photosensitive resin composition contains a photosensitizer, it may contain only one type of photosensitizer, or may contain two or more types of photosensitizers. When a photosensitizer is used, the amount used is, for example, 1 to 30 parts by mass, and preferably 3 to 20 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylate compound.

[0069] (Thermal Radical Initiator) The photosensitive resin composition of the present embodiment preferably contains a thermal radical initiator. By using the thermal radical initiator, it is easy to appropriately adjust the value of CTE2 / CTE1 described later, to further improve the reliability of electronic devices, and to further increase the heat resistance of the cured film. This is considered to be because the use of the thermal radical initiator further promotes the polymerization reaction of the polyfunctional (meth)acrylate compound.

[0070] The thermal radical initiator preferably includes an organic peroxide.The organic peroxide may 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, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, parachlorobenzoyl peroxide, cyclohexanone peroxide, etc.

[0071] When a thermal radical initiator is used, only one thermal radical initiator may be used, or two or more thermal radical initiators may be used. When a thermal radical initiator is used, the amount thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylate compound.

[0072] (Epoxy resin) The photosensitive resin composition of the present embodiment preferably contains an epoxy resin. Although the details are unclear, it is believed that the epoxy resin reacts (forms a bond) with, for example, a polyamide resin and / or a polyimide resin. And, the mechanical properties (such as tensile elongation) of the cured film tend to be improved, probably due to the flexibility of the ether structure formed by the reaction.

[0073] As the epoxy resin, any compound having one or more (preferably two or more) epoxy groups in one molecule can be appropriately used. Specific examples of epoxy resins include glycidyl ethers such as n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and glycidyl ether of bisphenol A (or F); glycidyl esters such as adipic acid diglycidyl ester and o-phthalic acid diglycidyl ester; 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate; 3,4-epoxy-6-methylcyclohexylmethyl ( 3,4-epoxy-6-methylcyclohexane)carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentanediene oxide, bis(2,3-epoxycyclopentyl)ether, alicyclic epoxy resins such as Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 8000, and Epolead GT401 manufactured by Daicel Corporation, 2,2'-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane)) (e.g., Techmore manufactured by Printec Co., Ltd. Examples of suitable polyglycidyl ethers include aliphatic polyglycidyl ethers such as VG3101L, Epolite 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.), and Epiol TMP (manufactured by NOF Corporation); and 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane (e.g., DMS-E09 (manufactured by Gelest Pharmaceuticals)).

[0074] The epoxy resin preferably has 2 to 4 epoxy groups in one molecule, and more preferably has 2 to 3 epoxy groups in one molecule. By adjusting the number of functional groups in the epoxy resin, it is easy to improve, for example, the heat resistance and mechanical properties of the cured film in a well-balanced manner. From another viewpoint, the epoxy resin preferably has an aromatic ring structure and / or an alicyclic structure. The use of such an epoxy resin is particularly preferable from the viewpoint of heat resistance.

[0075] When an epoxy resin is used, only one epoxy resin may be used, or two or more epoxy resins may be used in combination. When an epoxy resin is used, the amount thereof is, for example, 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass, relative to 100 parts by mass of the polyamide resin and / or polyimide resin.

[0076] (curing catalyst) The photosensitive resin composition of the present embodiment preferably contains a curing catalyst. The curing catalyst has a function of promoting the reaction of the epoxy resin. By using the curing catalyst, the reaction involving the epoxy resin can be sufficiently advanced, and for example, the tensile elongation of the cured film can be further improved.

[0077] Examples of the curing catalyst include compounds known as curing catalysts for epoxy resins (often also called curing accelerators). 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.

[0078] When a curing catalyst is used, the amount thereof is, for example, 1 to 80 parts by mass, and preferably 5 to 50 parts by mass, relative to 100 parts by mass of the epoxy resin.

[0079] (Silane coupling agent) The photosensitive resin composition of the present embodiment preferably contains a silane coupling agent. By using a silane coupling agent, for example, the adhesion between a substrate and a cured film can be further improved.

[0080] Examples of the silane coupling agent 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.

[0081] 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.

[0082] 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 polyamide resin and / or polyimide resin, and therefore a particularly good adhesion improving effect can be obtained.

[0083] When a silane coupling agent is used, it may be used alone or two or more kinds of adhesion assistants may be used in combination. When a silane coupling agent 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 polyamide resin and / or polyimide resin used.

[0084] (Surfactant) The photosensitive resin composition of the present embodiment preferably contains a surfactant, which can further improve the coatability of the photosensitive resin composition and the flatness of the film. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, an alkyl-based surfactant, and an acrylic-based surfactant.

[0085] The surfactant preferably contains at least one of a fluorine atom and a silicon atom, which contributes to obtaining a uniform resin film (improved coating properties) and improved developability, as well as improved adhesive strength. 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.

[0086] Commercially available surfactants that can be preferably used include, for example, the "Megafac" series manufactured by DIC Corporation, including 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, and F-566. fluorine-containing oligomer structure surfactants such as F-568, 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.

[0087] When the photosensitive resin composition of the present embodiment contains a surfactant, it may contain one or more surfactants. When the photosensitive resin composition of the present embodiment contains a surfactant, 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 polyamide resin and / or polyimide resin content.

[0088] (water) The photosensitive resin composition of the present embodiment may contain water. The presence of water, for example, facilitates the hydrolysis reaction of the silane coupling agent, and tends to further increase the adhesion between the substrate and the cured film.

[0089] When the photosensitive resin composition of this embodiment contains water, the amount of water is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.5 to 2 parts by mass, relative to 100 parts by mass of the total solid content (non-volatile components) of the photosensitive resin composition. The water content of the photosensitive resin composition can be determined by the Karl Fischer method.

[0090] (Solvent / Composition Properties) The photosensitive resin composition of the present embodiment preferably contains a solvent, 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 typically comprises an organic solvent. The solvent is not particularly limited so long as it can dissolve or disperse each of the above-mentioned components and does not substantially chemically react with each of the constituent components.

[0091] Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate. The solvents may be used alone or in combination.

[0092] When the photosensitive resin composition of the present embodiment contains a solvent, the photosensitive resin composition of the present embodiment is usually in a varnish state. More specifically, the photosensitive resin composition of the present embodiment is preferably a varnish-like composition in which at least a polyamide resin and / or a polyimide resin is dissolved in a solvent. Since the photosensitive resin composition of the present embodiment is in the form of a varnish, a uniform film can be formed by coating. In addition, since the polyamide resin and / or polyimide resin is "dissolved" in a solvent, a uniform cured film can be obtained.

[0093] When a solvent is used, the concentration of the total solids (non-volatile components) in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 45% by 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, the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of the non-volatile components. From another perspective, the ratio of the polyamide resin and / or polyimide resin and the polyfunctional (meth)acrylate compound in the entire composition is preferably 20 to 50 mass %. By using a relatively large amount of the polyamide resin and / or polyimide resin and the polyfunctional (meth)acrylate compound, a film of an appropriate thickness can be easily formed.

[0094] (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 an antioxidant, a filler such as silica, a sensitizer, a film-forming agent, etc.

[0095] (Various physical properties) Regarding the photosensitive resin composition of this embodiment, E' 220 In addition to designing the composition so that the compressive strength is 0.5 to 3.0 GPa, by satisfying other physical properties, further performance improvement can be achieved.

[0096] From one viewpoint, the reliability of electronic devices can be further improved by the appropriate thermal expansion behavior of the cured product of the photosensitive resin composition of the present embodiment. in particular, The glass transition temperature of the cured film obtained by heating the photosensitive resin composition at 170°C for 2 hours is Tg [°C]. The thermal expansion coefficient of the cured film in the temperature range from Tg-50[℃] to Tg-20[℃] is CTE1, When the thermal expansion coefficient of the cured film in the temperature range from Tg+20[°C] to Tg+50[°C] is CTE2, the value of CTE2 / CTE1 is preferably 1-10, more preferably 1-7, and even more preferably 1-5. By designing the photosensitive resin composition so that CTE2 is not excessively larger than CTE1, it is believed that the deterioration / softening of the cured film due to heating in the electronic device manufacturing process can be further suppressed, and the reliability of the electronic device can be further improved. Ideally, the value of CTE2 / CTE1 is preferably close to 1, but from the viewpoint of practical composition design, the lower limit is, for example, about 1.1.

[0097] By the way, the value of CTE1 itself is preferably 2×10 -5 ~8×10 -5 / °C, more preferably 2×10 -5 ~8×10 -5 / °C, and more preferably 3×10 -5 ~7×10 -5 / °C, and especially preferably 4×10 -5 ~6×10 -5 / ℃. In addition, the value of CTE2 itself is preferably 2×10 -5 ~100×10 -5 / °C, more preferably 2×10 -5 ~80×10 -5 / °C, and more preferably 5 × 10 -5 ~60×10 -5 / °C, and especially preferably 5 × 10 -5 ~50×10 -5 / ℃. The glass transition temperature Tg is preferably 170 to 270°C, more preferably 170 to 250°C, further preferably 200 to 250°C, and particularly preferably 210 to 230°C.

[0098] From a viewpoint different from the thermal expansion behavior of the cured product, the performance can be further improved by designing the storage modulus of the cured film of the photosensitive resin composition at 250 to 280° C. to an appropriate value. Specifically, this is as follows.

[0099] In the dynamic viscoelasticity measurement under the above-mentioned [Conditions], the storage modulus E' of the cured film of the photosensitive resin composition of this embodiment at 250 ° C. 250 is preferably 0.3 GPa or more, more preferably 0.3 GPa or more and 3.0 GPa or less, and further preferably 0.5 GPa or more and 2.0 GPa or less. In the dynamic viscoelasticity measurement under the above-mentioned [Conditions], the storage modulus E' at 280 ° C. of the cured film of the photosensitive resin composition of this embodiment 280is preferably 0.1 GPa or more, more preferably 0.1 GPa or more and 2.0 GPa or less, and further preferably 0.2 GPa or more and 1.0 GPa or less. E' 250 or E' 280 By designing the photosensitive resin composition so that the value falls within the above-mentioned range, it is believed that peeling of the cured film can be suppressed even in a reflow process that requires high temperatures, and the reliability of electronic devices can be further improved.

[0100] <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.

[0101] The film-forming step is usually carried out by applying a photosensitive resin composition onto a substrate, and can be carried out using a spin coater, a bar coater, a spray device, an inkjet device, or the like. Before the next exposure step, it is preferable to perform appropriate heating for the purpose of drying the solvent in the applied photosensitive resin composition, etc. The heating at this time is performed, for example, at a temperature of 80 to 150° C. for 1 to 60 minutes. The thickness of the photosensitive resin film after drying varies appropriately depending on the structure of the electronic device to be finally obtained, but is, for example, about 1 to 100 μm, specifically about 1 to 50 μm.

[0102] The exposure dose in the exposure step is not particularly limited.2 is preferable, and 200 to 1000 mJ / cm 2 is more preferred. The light source used for exposure is not particularly limited as long as it emits light of a wavelength (e.g., g-line or i-line) to which the photosensitizer in the photosensitive resin composition reacts. Typically, a high-pressure mercury lamp is used. If necessary, post-exposure baking may be performed. The temperature of the post-exposure baking is not particularly limited. It is preferably 50 to 150° C., more preferably 50 to 130° C., even more preferably 55 to 120° C., and particularly preferably 60 to 110° C. The time of the post-exposure baking is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, and even more preferably 1 to 15 minutes. In the exposure step, a photomask can be used, which allows a desired "pattern" to be formed using the photosensitive resin composition.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] The conditions for the heat curing step are not particularly limited, but may be, for example, a heating temperature of about 160 to 250° C. and a time of about 30 to 240 minutes.

[0108] A specific example of a method for manufacturing an electronic device will be described below with reference to the drawings. The specific example of the method for manufacturing an electronic device to be described is a method for sealing the semiconductor chip 40 from the side opposite to the side on which the electrode pads 30 are arranged, and is a method for manufacturing a so-called fan-out wafer-level package (FO-WLP) type electronic device.

[0109] 1(a), a semiconductor wafer that has been passivated in advance by forming a passivation film 50 thereon is diced into individual pieces to obtain a structure in which a plurality of semiconductor chips 40 are arranged at predetermined intervals, and the terminal surfaces (surfaces on which electrode pads 30 are arranged) of the semiconductor chips 40 are attached to the adhesive surface of an adhesive material 200. As a material for forming the passivation film 50, the photosensitive resin composition used for forming the first insulating resin film 60 described later can be used. In the structure of FIG. 1(a), the multiple semiconductor chips 40 are preferably embedded inside the sealing material 10 so that the electrode pads 30 provided on the surfaces of the multiple semiconductor chips 40 all face in the same direction. A pillar-shaped conductor made of a metal such as copper may be formed on the electrode pad 30 of the semiconductor chip 40. Furthermore, a solder bump may be formed on the end face of the conductor opposite to the side on which the electrode pad is disposed.

[0110] 1(b), the semiconductor chips 40 attached to the adhesive member 200 are covered and sealed with a cured product of the semiconductor sealing resin composition. In this embodiment, the cured product of the semiconductor sealing resin composition refers to a sealing material. As the semiconductor sealing resin composition, a known material can be used, and examples thereof include an epoxy resin composition containing an epoxy resin, an inorganic filler, and a curing agent.

[0111] Examples of methods for encapsulating the semiconductor chip 40 using the semiconductor encapsulation resin composition include transfer molding, compression molding, injection molding, lamination, and the like. Among them, from the viewpoint of forming the encapsulant 10 without leaving any unfilled portion, the transfer molding, compression molding, or lamination method is preferred. Therefore, the semiconductor encapsulation resin composition used in this manufacturing method is preferably in the form of granules, powder, tablets, or sheets. Moreover, from the viewpoint of suppressing the occurrence of positional deviation of the semiconductor chip 40 during molding of the encapsulant 10, the compression molding method is particularly preferred.

[0112] Next, as shown in FIG. 1(c), the adhesive member 200 is peeled off. In this way, a structure in which a plurality of semiconductor chips 40 having electrode pads 30 on their surfaces are embedded inside the sealing material 10 can be obtained. It is preferable that the adhesive member 200 is peeled off from the structure after the adhesion between the adhesive member 200 and the structure is reduced. Specifically, a method of reducing the adhesion by deteriorating the adhesive layer of the adhesive member 200 forming the adhesion site by, for example, irradiating the adhesion site between the adhesive member 200 and the structure with ultraviolet light or performing heat treatment can be exemplified. The adhesive member 200 is not particularly limited as long as it adheres to the semiconductor chip 40, but an example of the adhesive member 200 is a member formed by laminating a backgrind tape and an adhesive layer. The structure shown in FIG. 1(c) relates to an embodiment in which the surface of the semiconductor chip 40 opposite the surface on which the electrode pads 30 are arranged is covered with the sealing material 10. However, in this manufacturing method, before peeling off the adhesive material 200, a step may be included in which the sealing material 10 is polished and removed by a known method so as to expose the surface of the semiconductor chip 40 opposite the surface on which the electrode pads 30 are arranged.

[0113] Next, as shown in FIG. 2(a), a first insulating resin film 60 is formed on the surface of the obtained structure on the side where the electrode pads 30 are embedded. Specifically, a varnish-like resin composition is applied to the surface of the above-mentioned structure on the side where the electrode pads 30 are embedded, and then dried to form the first insulating resin film 60. The film thickness of the first insulating resin film 60 can be, for example, 1 to 300 μm. As a method for applying the resin composition, known methods such as spin coating, slit coating, and inkjet can be used. Among these, it is preferable to adopt the spin coating method.

[0114] In this manufacturing method, it is preferable to use the above-mentioned photosensitive resin composition (the composition explained in the <Photosensitive resin composition> section) as the resin material constituting the first insulating resin film 60.

[0115] In this manufacturing method, it is preferable to perform plasma treatment on the surface of the sealing material 10 on which the first insulating resin film 60 is to be formed, before forming the first insulating resin film 60. This can improve the wettability of the first insulating resin film 60. As a result, the adhesion between the sealing material 10 and the first insulating resin film 60 can be further improved. In the plasma treatment, for example, argon gas, oxidizing gas, or fluorine-based gas can be used as the treatment gas. Examples of the oxidizing gas include O2 gas, O3 gas, CO gas, CO2 gas, NO gas, and NO2 gas. For example, an oxidizing gas is preferably used as the treatment gas. Also, for example, an O2 gas is preferably used as the oxidizing gas. This allows specific functional groups to be formed on the surface of the sealing material 10. Therefore, the adhesion and coatability of the first insulating resin film 60 to the sealing material 10 can be further improved, and the reliability of the electronic device can be further improved.

[0116] The conditions of the plasma treatment are not particularly limited, but may be an ashing treatment or a treatment in which the target is exposed to plasma derived from an inert gas. The plasma treatment according to the present manufacturing method is preferably a plasma treatment performed without applying a bias voltage to the target, or a plasma treatment performed using a non-reactive gas. In the present manufacturing method, a chemical treatment may be performed instead of the plasma treatment, or both the plasma treatment and the chemical treatment may be performed. Examples of chemicals that can be used in the chemical treatment include an aqueous solution of an alkaline permanganate such as potassium permanganate or sodium permanganate.

[0117] 2(b), a first opening 250 is formed in the first insulating resin film 60 to expose a part of the electrode pad 30. The first opening 250 can be formed by exposure and development or laser processing. In addition, the formed first opening 250 is preferably subjected to a descum treatment to remove scum (resin residue) generated when the first opening 250 is formed.

[0118] The descum treatment may be performed by plasma irradiation, using, for example, argon gas, O2 gas, O3 gas, CO gas, CO2 gas, NO gas, NO2 gas, or a fluorine-based gas as the treatment gas.

[0119] 2(c), a conductive film 110 is formed so as to cover the exposed electrode pads 30 and the first insulating resin film 60. The conductive film 110 may be, for example, any one of an electrolytic copper plating film, a solder plating film, a tin plating film, a plating film having a two-layer structure in which a gold plating film is laminated on a nickel plating film, and an under bump metal (UBM) film formed by electroless plating. The thickness of the conductive film 110 may be, for example, 2 to 10 μm. From the viewpoint of improving the durability of the finally obtained electronic device 100, the surface of the obtained conductive film 110 may be subjected to a plasma treatment in the same manner as described above.

[0120] As the plating method, for example, electrolytic plating or electroless plating can be adopted. When electroless plating is used, the conductive film 110 can be formed as follows. In the following, an example of forming the conductive film 110 consisting of two layers of nickel and gold will be described, but the present invention is not limited to this. First, a nickel plating film is formed. When electroless nickel plating is performed, the structure shown in FIG. 2(b) is immersed in a plating solution. In this way, a conductive film 110 can be formed on the surface of the electrode pad 30 and the first insulating resin film 60. The plating solution may contain nickel lead and, for example, hypophosphite as a reducing agent. Next, electroless gold plating is performed on the nickel plating film. The method of electroless gold plating is not particularly limited, but it can be performed by, for example, displacement gold plating, which is performed by replacing gold ions with ions of the base metal.

[0121] In this way, in the FO-WLP, the semiconductor chip 40 is embedded in the encapsulant 10. The circuit surface of the semiconductor chip 40 is exposed to the outside, and a boundary between the semiconductor chip 40 and the encapsulant 10 is formed. A conductive film 110 (rewiring layer) connected to the electrode pads 30 of the semiconductor chip 40 is also provided in the region of the encapsulant 10 in which the semiconductor chip 40 is embedded, and the bumps are electrically connected to the electrode pads 30 of the semiconductor chip 40 via the conductive film 110 (rewiring layer). The pitch of the bumps can be set larger than the pitch of the electrode pads 30 of the semiconductor chip 40.

[0122] Next, as shown in Fig. 3(a), a second insulating resin film 70 is formed on the surface of the conductive film 110. Thereafter, in this embodiment, as shown in Fig. 3(b), a second opening 300 is formed to expose a part of the conductive film 110. The second insulating resin film 70 and the second opening 300 can be formed by the same method as the method for forming the first insulating resin film 60 and the first opening 250. The material for forming the second insulating resin film 70 can be the photosensitive resin composition used for forming the first insulating resin film 60 (i.e., the composition described in the <Photosensitive resin composition> section).

[0123] 3(c), the solder bump 80 or the end of the bonding wire is melted and fused onto the conductive film 110 exposed in the second opening 300. In this manner, the electronic device 100 according to this embodiment can be obtained. Thereafter, although not shown, the electronic device 100 can be cut along dicing lines formed on the electronic device 100 so as to include at least one semiconductor chip 40, thereby dividing the electronic device 100 into a plurality of semiconductor packages (electronic devices).

[0124] In addition, in this manufacturing method, starting from the structure shown in Fig. 3(b), an electronic device having a multilayer wiring structure in which conductive films (wiring layers) and insulating resin films are laminated in this order can also be manufactured. According to this manufacturing method, for example, an electronic device having four conductive films (wiring layers) and five insulating resin films can also be manufactured. In this case, the conductive films (wiring layers) can be formed using the same method as the method for forming the conductive film 110. Furthermore, the insulating resin film can be formed using the same method as the method for forming the first insulating resin film 60. When manufacturing an electronic device having the above-mentioned multilayer wiring structure, the obtained electronic device can be electrically connected by melting the ends of solder bumps 80 or bonding wires on the outermost layer and fusing them to the conductive film (wiring layer) in a manner similar to that described above.

[0125] This manufacturing method involves a technique for starting with the structure shown in Figure 1(c) and forming an insulating resin film and a conductive film (wiring layer) on only one surface of the structure, but if the structure shown in Figure 1(c) is in a state in which the surface opposite to the side on which the electrode pads 30 of the semiconductor chip 40 are arranged is also exposed, an insulating resin film may be formed on both surfaces of the structure.

[0126] This manufacturing method can be applied to a process for producing chip-sized semiconductor packages, but from the viewpoint of improving the productivity of semiconductor packages, it may also be applied to a process for producing so-called wafer-level packages, or a process for producing panel-level packages that assume the use of large-area panels larger than the wafer size.

[0127] 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. Below, examples of reference forms are given. 1. A photosensitive resin composition containing a polyamide resin and / or a polyimide resin, The photosensitive resin composition was heated at 170°C for 2 hours to obtain a cured film, and the dynamic viscoelasticity was measured under the following conditions. The storage modulus E' at 220°C was 220 The photosensitive resin composition has a compressive strength of 0.5 to 3.0 GPa. [conditions] Frequency: 1Hz Temperature: 30~300℃ Heating rate: 5℃ / min Measurement mode: Tensile mode 2. 1. The photosensitive resin composition according to claim 1, The glass transition temperature of the cured film is Tg [°C], A photosensitive resin composition, in which the value of CTE2 / CTE1 is 1 to 10, where CTE1 is the thermal expansion coefficient of the cured film in the temperature range from Tg-50 [°C] to Tg-20 [°C] and CTE2 is the thermal expansion coefficient of the cured film in the temperature range from Tg+20 [°C] to Tg+50 [°C]. 3. 1. The photosensitive resin composition according to 1. or 2. A photosensitive resin composition comprising a polyimide resin having an imide ring structure. 4. The photosensitive resin composition according to any one of 1. to 3., The photosensitive resin composition further comprises a polyfunctional (meth)acrylate compound. 5. The photosensitive resin composition according to any one of 1. to 4., The photosensitive resin composition further comprises a photosensitizer. 6. 5. The photosensitive resin composition according to claim 5, The photosensitive resin composition, wherein the photosensitizer contains a photoradical generator. 7. The photosensitive resin composition according to any one of 1. to 6, The photosensitive resin composition further comprises a thermal radical initiator. 8. 1. The photosensitive resin composition according to any one of claims 1 to 7, The photosensitive resin composition further comprises an epoxy resin. 9. 1. The photosensitive resin composition according to any one of claims 1 to 8, A photosensitive resin composition in the form of a varnish in which at least the polyamide resin and / or polyimide resin is dissolved in a solvent. 10. The photosensitive resin composition according to any one of 1. to 9., A photosensitive resin composition used to form insulating layers in electronic devices. 11. a film-forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of 1. to 10.; 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: 12. 11. A method for producing an electronic device according to claim 10, further comprising the steps of: A method for producing an electronic device, comprising the steps of: after the developing step, a thermal curing step of heating and curing the exposed photosensitive resin film. 13. An electronic device comprising a cured film of the photosensitive resin composition according to any one of 1. to 10. EXAMPLES

[0128] 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, "DMAc" is the abbreviation for dimethylacetamide. Other abbreviations will be explained as appropriate in the text.

[0129] <Polymer synthesis> (Synthesis of Polymer (A-1)) A 3L glass separable flask equipped with a stirrer and agitator was charged with 64.1g (0.20 mol) of TFMB (2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl), 97.7g (0.22 mol) of 6FDA (4,4'-(hexafluoroisopropylidene)diphthalic dianhydride), and 500g of DMAc, and stirred to dissolve TFMB and 6FDA in DMAc. The mixture was further stirred at room temperature for 12 hours under a nitrogen stream to carry out the polymerization reaction, yielding a polyamic acid solution.

[0130] After adding 16 g of pyridine to the obtained polyamic acid solution, 82 g of acetic anhydride was added dropwise at room temperature, and the liquid temperature was kept at 20 to 100° C. and the mixture was stirred for 24 hours to carry out an imidization reaction, thereby obtaining a polyimide solution.

[0131] The obtained polyimide solution was poured into 1,000 g of methanol in a 5 L container while stirring to precipitate the polyimide resin. The solid polyimide resin was then filtered using a suction filter and washed with 1,000 g of methanol. It was then dried at 100°C for 24 hours using a vacuum dryer, and then dried at 200°C for 3 hours. As a result, a polymer (A-1) was obtained, which is a polyimide powder having an acid anhydride group at the end. The weight average molecular weight (Mw) of the polymer (A-1) measured by GPC was 25,000. In addition, the polymer (A-1) 1 H-NMR was measured, and the imidization rate (defined above) was calculated from the quantitative value of the amide peak relative to the peak of the aromatic ring of the polyimide. The imidization rate was 99% or more.

[0132] (Synthesis of Polymer (A-2)) Polymer synthesis was carried out in the same manner as for polymer (A-1), except that 56.4 g (0.176 mol) of TFMB and 12.4 g (0.024 mol) of BAPP-F<2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane> were used instead of 64.1 g (0.20 mol) of TFMB. Then, polymer (A-2), which is a polyimide powder having an acid anhydride group at the terminal, was obtained. The weight average molecular weight (Mw) of the polymer (A-2) measured by GPC was 26,000. The imidization rate of the polymer (A-2) measured by NMR was 99% or more.

[0133] (Synthesis of Polymer (A-3)) Polymer synthesis was carried out in the same manner as for polymer (A-1), except that 6FDA 78.2g (0.176mol) and ODPA <4,4'-oxydiphthalic dianhydride> 13.7g (0.044mol) were used instead of 6FDA 97.7g (0.22mol). Thus, polymer (A-3), which is a polyimide powder having an acid anhydride group at the terminal, was obtained. The weight average molecular weight (Mw) of the polymer (A-3) measured by GPC was 24,000. The imidization rate of the polymer (A-3) measured by NMR was 99% or more.

[0134] (Synthesis of Polymer (A-4)) Polymer synthesis was carried out in the same manner as for polymer (A-1), except that 83.1 g (0.187 mol) of 6FDA and 9.71 g (0.033 mol) of BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride) were used instead of 97.7 g (0.22 mol) of 6FDA. Polyimide resin (A-4) having acid anhydride groups at the terminals was obtained. The weight average molecular weight (Mw) of the polymer (A-4) measured by GPC was 24,000. The imidization rate of the polymer (A-4) measured by NMR was 99% or more.

[0135] (Synthesis of Polymer (A-5)) A polymer was synthesized in the same manner as for polymer (A-1), except that 85.7 g (0.20 mol) of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene was used instead of 64.1 g (0.20 mol) of TFMB, and polymer (A-5), which is a polyimide powder having an acid anhydride group at the terminal, was obtained. The weight average molecular weight (Mw) of the polymer (A-5) measured by GPC was 25,000. The imidization rate of the polymer (A-5) measured by NMR was 99% or more.

[0136] <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.

[0137] Details of the raw materials for each component in Table 1 are as follows:

[0138] <Polyamide resin and / or polyimide resin> (A-1) Polymer synthesized above (A-2) Polymer synthesized above (A-3) Polymer synthesized above (A-4) Polymer synthesized above (A-5) Polymer synthesized above

[0139] The structures of each of the above polymers are shown below.

[0140] [ka]

[0141] <Polyfunctional (meth)acrylate compounds> (B-1) Viscoat #802 (Osaka Organic Industry Co., Ltd., a mixture of compounds having 5 to 10 acryloyl groups per molecule) (B-2) NK Ester A-9550 (manufactured by Shin-Nakamura Chemical Co., Ltd., a mixture of compounds having 5 to 6 acryloyl groups per molecule) (B-3) Viscoat #300 (Osaka Organic Industry Co., Ltd., a mixture of compounds having 3 to 4 acryloyl groups per molecule) (B-4) Viscoat #230 (Osaka Organic Industry Co., Ltd., a compound having two acryloyl groups per molecule)

[0142] The structures of the above (B-1) to (B-4) are shown below.

[0143] [ka]

[0144] <Photosensitizer> (C-1) Irugacure OXE01 (BASF, oxime ester type photoradical generator) (C-2) ADEKA ARCLES NCI-730 (manufactured by ADEKA Corporation, oxime ester type photoradical generator)

[0145] <Thermal radical generator> (D-1) Perkadox BC (manufactured by Nouryon Chemical Industries, Ltd., organic peroxide, dicumyl peroxide)

[0146] <Epoxy resin> (E-1) TECHMORE VG3101L (manufactured by Printec Co., Ltd.) (E-2) Celoxide 2021P (manufactured by Daicel Corporation)

[0147] <Curing catalyst> (F-1) Tetraphenylphosphonium 4,4'-sulfonyldiphenolate The curing catalyst (F-1) was 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, the target product was obtained as a white crystal.

[0148] <Silane coupling agent> (G-1) KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent containing a (meth)acryloyl group) (G-2) X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent having a cyclic anhydride structure)

[0149] <Surfactant> (H-1) FC4432 (3M, fluorine-based)

[0150] <Solvent> (J-1) Ethyl lactate (EL) (J-2) γ-butyrolactone (GBL)

[0151] <Dynamic viscoelasticity measurement of cured film (E' 220 etc.)> (Preparation of test specimens) 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 coating film. The resulting coating was irradiated with 1000 mJ / cm 2 of high pressure mercury lamp. 2 The film was then exposed to light for 30 seconds at 120°C. After that, the film was baked for 30 seconds in cyclopentanone. After that, the film was heated for 2 hours at 170°C in a nitrogen atmosphere for curing. As a result, a cured film 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. The cut product was immersed in a 2 mass % aqueous solution of hydrofluoric acid to peel off the cured film from the wafer. The peeled cured film was dried at 60° C. for 10 hours to obtain a test piece (30 mm×5 mm×10 μm thick).

[0152] The obtained test pieces were heated from 30°C to 300°C under nitrogen atmosphere at a frequency of 1Hz, in tension mode, and at a heating rate of 5°C / min using a dynamic viscoelasticity measuring device (TA, Q800), to measure the storage modulus versus temperature. From the obtained storage modulus (E') curve, the storage modulus [MPa] at 220°C, 250°C, and 280°C was read.

[0153] <Measurement of thermal expansion coefficient and glass transition temperature (Tg)> Using a thermomechanical analyzer (Seiko Instruments Inc., TMA / SS6000), the test piece obtained in the same manner as in the dynamic viscoelasticity measurement of the cured film was heated to 300°C at a heating rate of 10°C / min. The relationship between temperature and displacement at this time was graphed. The glass transition temperature (Tg) of the cured product was determined from the position of the inflection point of the obtained graph. In addition, the linear expansion coefficient in the region from Tg-50[℃] to Tg-20[℃] in the obtained graph was determined as CTE1, and the linear expansion coefficient in the region from Tg+20[℃] to Tg+50[℃] was determined as CTE2. The value of CTE2 / CTE1 was then calculated.

[0154] <Reliability evaluation (temperature cycle test)> (Creating a board for reliability evaluation) The photosensitive resin composition was spin-coated onto a 12-inch silicon wafer so that the film thickness after drying would be 5 μm, and then heated at 120° C. for 3 minutes to obtain a coating film. The resulting coating was irradiated with 1000 mJ / cm 2 of high pressure mercury lamp. 2 The film was then exposed to light for 30 seconds at 120°C. After that, the film was baked for 30 seconds in cyclopentanone. After that, the film was heated for 2 hours at 170°C in a nitrogen atmosphere for curing. This resulted in a first layer of a cured film of the photosensitive resin composition. On the obtained cured film, Ti and Cu were deposited by sputtering to a thickness of 500 Å and 3000 Å, respectively. Then, Cu wiring was created to a height of 5 μm by electrolytic plating through the resist. After peeling off the resist layer, the sputtered Cu and sputtered Ti were etched to create Cu wiring with a line / space of 2 μm / 2 μm. Next, the photosensitive resin composition was treated in the same manner as for the first layer, except that the film thickness was changed to 10 μm, to obtain a substrate for reliability evaluation.

[0155] (Reliability test) The substrate for reliability evaluation obtained as described above was set in a temperature cycle test apparatus (TCT apparatus) and subjected to 1000 cycles of heating from -60°C to 200°C and then cooling to -60°C, each cycle consisting of one cycle. Next, a cross section of the Cu wiring portion was exposed by FIB (focused ion beam) processing and observed by SEM. In each of the examples and comparative examples, a total of 10 interfaces between the wiring and the resin film were observed. If no peeling was observed in any of the 10 locations, the result was rated as ◎ (very good), if peeling was observed in one or two of the 10 locations, it was rated as ○ (good), and if peeling was observed in three or more locations, it was rated as × (bad).

[0156] <Evaluation of insulation reliability> (Preparation of insulation reliability samples) A Cu wiring substrate was fabricated on a silicon wafer with an oxide film by forming comb-shaped Cu wiring with a width of 5 μm, a pitch of 5 μm, and a height of 5 μm. The photosensitive resin composition was applied onto the Cu wiring substrate by spin coating so that the film thickness after drying (thickness of the part without wiring) would be 10 μm, and the composition was dried at 120° C. for 3 minutes to form a photosensitive resin film. The resulting photosensitive resin film was exposed to 300 mJ / cm 2 of light using a high-pressure mercury lamp. 2 The film was then exposed to light for 30 seconds. It was then immersed in cyclopentanone for 30 seconds. It was then heat-treated at 170°C for 2 hours in a nitrogen atmosphere to obtain a cured film. This was used as a sample for evaluating insulation reliability.

[0157] (Insulation reliability evaluation) A simulated electronic device for evaluation was fabricated by soldering the end of the Cu wiring (Cu electrode) of the substrate fabricated in the above (Insulation Reliability Sample Fabrication) to the electrode wiring. This was placed in an environment of 130°C / 85%RH while applying a bias of 3.5V in a B-HAST device. The insulation resistance between the Cu wiring of the Cu wiring board was automatically measured at 6-minute intervals, and insulation breakdown was deemed to have occurred when the insulation resistance value fell to 1.0 x 104 Ω or less. The time from the start of the test to insulation breakdown was then measured. In the table below, this time is marked as ◎ (very good) if it was 210 hours or more, ○ (good) if it was 50 to 210 hours, and × (bad) if it was less than 50 hours.

[0158] <Evaluation of shear strength at 250℃> Using the same method as in the above <Evaluation of patterning ability>, a 100μm×100μm remaining pattern was created on an 8-inch silicon wafer with a copper plating film. After that, a curing treatment was performed at 170℃ for 2 hours in a nitrogen atmosphere to obtain a sample for shear strength measurement. The obtained samples were measured for shear strength (heated shear strength, unit: MPa) at 250°C using a die shear device (Nordson, Dage-4000) under conditions of a shear speed of 200 nm / sec and a shear height of 1 μm. A large value means that the cured film is less likely to peel off even when exposed to high temperatures. In other words, a large value is preferable in terms of the reliability of electronic devices.

[0159] <Evaluation of cure shrinkage rate> 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 obtained photosensitive resin film was exposed to 300 mJ / cm2 with a high pressure mercury lamp. After that, it was immersed in cyclopentanone for 30 seconds, and then dried by spin drying to obtain a developed film of the photosensitive resin composition. The film thickness of this developed film was measured and was taken as film thickness A. The developed film was then cured by heat treatment at 170° C. for 2 hours in a nitrogen atmosphere. A cured film of the photosensitive resin composition was obtained as described above. The thickness of this cured film was measured and designated as film thickness B. The cure shrinkage was calculated by substituting the film thickness A and film thickness B into the following formula. The cure shrinkage is preferably small in order to maintain flatness after application onto wiring. Curing shrinkage rate [%] = {(film thickness A - film thickness B) / film thickness A} x 100

[0160] <Evaluation of flatness during application (flatness of step filling)> A Cu wiring board was fabricated by forming Cu wiring with a width of 5 μm, a pitch of 5 μm, and a height of 5 μm on a silicon wafer with an oxide film. A photosensitive resin composition was applied to the Cu wiring board by spin coating so that the film thickness after drying would be 10 μm, and the composition was dried at 120° C. for 3 minutes to form 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 substrate was immersed in cyclopentanone for 30 seconds, and then heat-treated at 170°C for 2 hours in a nitrogen atmosphere to form a cured film on the substrate. The obtained substrate with the cured film was split, and the cross section was polished and observed by SEM to evaluate the surface unevenness of the photosensitive resin film. Surface unevenness of 1 μm or less was evaluated as ○ (good), surface unevenness of 1 to 3 μm was evaluated as △ (usable level), and surface unevenness of over 3 μm was evaluated as × (bad).

[0161] <Evaluation of tensile elongation> First, the dynamic viscoelasticity measurement (E' 220 Test pieces were prepared in the same manner as in (Preparation of test pieces) of > Measurement of surface roughness, etc. The obtained test pieces were subjected to a tensile test 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 pieces was measured. The elongation speed in the tensile test was 5 mm / min.

[0162] <Evaluation of patterning ability> The photosensitive resin composition was applied onto an 8-inch silicon wafer using a spin coater so that the film thickness after drying would be 5 μm. Then, the composition was dried on a hot plate at 120° C. for 3 minutes to obtain a photosensitive resin film (photosensitive resin film A). This photosensitive resin film was irradiated with i-line using a mask manufactured by Toppan Printing Co., Ltd. (Test Chart No. 1: with patterns with 0.5 to 50 μm widths of left and right cut patterns drawn) while varying the exposure dose using an i-line stepper (Nikon Corporation, NSR-4425i). Thereafter, the film was developed for 30 seconds using cyclopentanone as a developer, spun at 2500 rpm for 10 seconds, and dried to obtain a developed film (negative pattern). Those in which a 7 μmφ via hole was opened were rated as ⊚ (very good), those in which a 10 μmφ via hole was opened were rated as ○ (good), and those in which a 10 μmφ via hole was not opened were rated as × (bad).

[0163] The composition of the raw materials for each composition and the measurement / evaluation results are summarized in Table 1.

[0164] [Table 1]

[0165] As shown in Table 1, the photosensitive resin compositions of Examples 1 to 14 (containing a polyamide resin and / or a polyimide resin, E' 220 The results of the temperature cycle test at a pressure of 0.5 to 3.0 GPa, the evaluation results of the insulation reliability, and the shear strength at 250° C. were all good. These evaluation results show that a highly reliable electronic device can be manufactured by curing the photosensitive resin composition of the present embodiment by heating at about 170° C. to form a cured film. The cured products of the photosensitive resin compositions of Examples 1 to 14 had small cure shrinkage rates and good flatness when filling steps. The cured products of the photosensitive resin compositions of Examples 1 to 14 had moderate elongation. In addition, the photosensitive resin compositions of Examples 1 to 14 had sufficient patterning performance when manufacturing electronic devices.

[0166] Looking more closely at the examples, the following can be seen. Comparing Example 11 with other Examples, the use of a thermal radical generator tends to increase the glass transition temperature of the cured product and to decrease CTE2 / CTE1. The use of a thermal radical generator also tends to improve reliability. This is probably because the use of a thermal radical generator further promotes the polymerization of the polyfunctional (meth)acrylate compound. Comparing Examples 12 and 13 with other Examples, the use of epoxy resin and its curing catalyst tends to improve the tensile elongation. It is believed that the polyamide resin and / or polyimide resin bond (crosslink) with the epoxy resin to form a cured film that is more stretchable and less likely to break. Comparing Example 14 with the other Examples, it is believed that the presence of water probably enhances the function of the adhesion aid, improving adhesion.

[0167] On the other hand, E' 220The evaluation results of the photosensitive resin composition of Comparative Example 1, in which the compressive strength was less than 0.50 GPa, were inferior to the evaluation results of the photosensitive resin compositions of Examples 1-14. [Explanation of symbols]

[0168] 10. Encapsulating material 30 Electrode Pads 40 Semiconductor Chips 50 Passivation film 60 Insulating resin film (first insulating resin film) 70 Insulating resin film (second insulating resin film) 80 Solder Bumps 100 Electronic Devices 110 Conductive film 200 Adhesive material 250 opening (first opening) 300 opening (second opening)

Claims

1. A photosensitive resin composition comprising a polyamide resin or a polyimide resin, and a polyfunctional (meth)acrylate compound which is a component different from the polyamide resin or the polyimide resin and is not a surfactant, The photosensitive resin composition contains only one of the polyamide resin or polyimide resin and further contains an epoxy resin, but does not contain any other resins; The photosensitive resin composition was heated at 170° C. for 2 hours to obtain a cured film, and the dynamic viscoelasticity was measured under the following conditions. The storage modulus E′ at 220° C. was ２２０ The photosensitive resin composition has a modulus of 0.5 to 3.0 GPa. [conditions] Frequency: 1Hz Temperature: 30-300℃ Heating rate: 5° C. / min Measurement mode: Tensile mode

2. The photosensitive resin composition according to claim 1, The glass transition temperature of the cured film is Tg [°C], A photosensitive resin composition, in which the value of CTE2 / CTE1 is 1 to 10, wherein the thermal expansion coefficient of the cured film in the temperature range from Tg-50 [°C] to Tg-20 [°C] is CTE1 and the thermal expansion coefficient of the cured film in the temperature range from Tg+20 [°C] to Tg+50 [°C] is CTE2.

3. The photosensitive resin composition according to claim 1 or 2, A photosensitive resin composition comprising a polyimide resin having an imide ring structure.

4. The photosensitive resin composition according to any one of claims 1 to 3, The photosensitive resin composition further comprises a photosensitizer.

5. The photosensitive resin composition according to claim 4, The photosensitive resin composition, wherein the photosensitizer contains a photoradical generator.

6. The photosensitive resin composition according to any one of claims 1 to 5, The photosensitive resin composition further comprises a thermal radical initiator.

7. The photosensitive resin composition according to any one of claims 1 to 6, A photosensitive resin composition in the form of a varnish in which at least the polyamide resin or polyimide resin is dissolved in a solvent.

8. The photosensitive resin composition according to any one of claims 1 to 7, A photosensitive resin composition used to form insulating layers in electronic devices.

9. 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 8; 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:

10. 10. The method of claim 9, further comprising the steps of: A method for producing an electronic device, comprising the steps of: after the developing step, a thermal curing step of heating and curing the exposed photosensitive resin film.

11. An electronic device comprising a cured film of the photosensitive resin composition according to any one of claims 1 to 10.

Images