Photosensitive resin composition, method for manufacturing 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 studied.

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

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

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

[0006] With the advancement and complexity of electronic devices, higher reliability than ever is required for electronic devices. Therefore, it is required to improve the reliability of electronic devices by improving the cured film (improving the photosensitive resin composition for forming the cured film). In recent years, in order to reduce thermal damage to semiconductor chips, it has been required to relatively lower the heating temperature when forming the cured film (for example, to about 170°C).

[0007] The present invention has been made in view of such circumstances. One of the objects of the present invention is to provide a photosensitive resin composition capable of manufacturing a highly reliable electronic device by curing at about 170°C to form a cured film. [Means for Solving the Problems]

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

[0009] According to the present invention, the following photosensitive resin composition is provided. A photosensitive resin composition containing a polyamide resin and / or a polyimide resin, When the cured film obtained by heating the photosensitive resin composition at 170°C for 2 hours is subjected to dynamic viscoelasticity measurement under the following conditions, the storage elastic modulus E' at 220°C 220 is 0.5 to 3.0 GPa, the photosensitive resin composition. [Conditions] Frequency: 1 Hz Temperature: 30 to 300°C Temperature rising rate: 5°C / min Measurement mode: Tensile mode

[0010] Also, according to the present invention, A film forming step of forming a photosensitive resin film on a substrate using the above photosensitive resin composition, An exposure step of exposing the photosensitive resin film; A development step of developing the exposed photosensitive resin film; A method for manufacturing an electronic device, including the above steps. is provided.

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

Advantages of the Invention

[0012] By curing the photosensitive resin composition of the present invention by heating at about 170 ° C. to form a cured film, it is possible to manufacture a highly reliable electronic device.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0014] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and the description thereof will be omitted as appropriate. To avoid complexity, (i) when there are a plurality of the same components in the same drawing, only one of them is denoted by a reference numeral, and all of them may not be denoted by a reference numeral, or (ii) particularly in FIGS. 2 and later, the same components as those in FIG. 1 may not be denoted by a reference numeral again. All the drawings are for explanatory purposes only. The shapes and dimensional ratios of the members in the drawings do not necessarily correspond to actual articles.

[0015] In this specification, unless otherwise explicitly stated, the term "approximate" indicates that it includes the range considering manufacturing tolerances, assembly variations, etc. In this specification, the notation "X~Y" in the description of a numerical range represents X or more and Y or less, unless otherwise specified. For example, "1~5 mass%" means "1 mass% or more and 5 mass% or less".

[0016] In the notation of a group (atomic group) in this specification, the notation without indicating whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The notation "(meth)acrylic" in this specification represents a concept including both acrylic and methacrylic. The same applies to similar notations such as "(meth)acrylate". In this specification, the term "organic group" means, unless otherwise specified, an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, the "monovalent organic group" represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound. In this specification, the term "electronic device" is used to mean elements, devices, end products, etc. to which the technology of electronics is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information communication terminals, light-emitting diodes, physical batteries, chemical batteries, etc.

[0017] <Photosensitive resin composition> The photosensitive resin composition of this embodiment contains a polyamide resin and / or a polyimide resin. The storage modulus E' at 220°C when a cured film obtained by heating the photosensitive resin composition of this embodiment at 170°C for 2 hours is subjected to dynamic viscoelasticity measurement under the following conditions 220 is 0.5~3.0 GPa. [Conditions] Frequency: 1 Hz Temperature: 30~300°C Heating rate: 5°C / min Measurement mode: Tensile mode

[0018] In the process of manufacturing electronic devices, various "heating" operations are performed, which may cause the cured film to reach a high temperature. The inventors considered that the high temperature due to heating might have an adverse effect on the cured film in the electronic device, resulting in a decrease in the reliability of the electronic device. More specifically, since the cured film deteriorates / softens at high temperatures, for example, the adhesion between the cured film and the substrate decreases and the cured film peels off, resulting in a decrease in the reliability of the electronic device.

[0019] Based on this idea, the inventors thought that if a photosensitive resin composition capable of forming a cured film that is difficult to soften (the elastic modulus at ≒220°C is relatively large) at 220°C, which can be adopted as the heating temperature in heating such as the reflow process, could be designed, the decrease in the adhesion of the cured film due to heating could be suppressed, and as a result, the reliability of the electronic device would be enhanced. Also, if such a cured film could be formed by heating at about 170°C, it could follow the trend of recent electronic device manufacturing.

[0020] Taking this idea further, the inventors, in a photosensitive resin composition containing a polyamide resin and / or a polyimide resin, (i) adopted the storage elastic modulus E' of the cured film at 220°C as an index of the difficulty of softening of the cured film at 220°C 220 and (ii) newly designed a photosensitive resin composition in which the E' 220 is 0.5 GPa or more. Here, as the conditions for forming the cured film, "170°C for 2 hours" was adopted based on the trend in recent electronic device manufacturing. By applying this new photosensitive resin composition to the manufacture of electronic devices (such as forming an insulating layer in an electronic device), the inventors succeeded in enhancing the reliability of the electronic device.

[0021] Incidentally, in principle, E' 220Although it is generally considered that the larger E' is, the better it is, from the perspective of cost and practical composition design, in this embodiment, the upper limit of E' 220 is set to 3.0 GPa. E' 220 may be in the range of 0.5 to 3.0 GPa, preferably 0.6 to 2.5 GPa, and more preferably 0.7 to 2.0 GPa.

[0022] The photosensitive resin composition of this embodiment, where E' 220 is 0.5 GPa or more and 3.0 GPa or less, can be manufactured by appropriately selecting materials, their formulations, preparation methods, etc. Preferred materials for the photosensitive resin composition of this embodiment will be described below. For example, when used in combination with a polyamide resin and / or a polyimide resin, appropriate polyfunctional (meth)acrylates can be selected.

[0023] Continue the description of the photosensitive resin composition of this embodiment.

[0024] (Polyamide resin and / or polyimide resin) The photosensitive resin composition of this embodiment contains a polyamide resin and / or a polyimide resin. As long as E' 220 is in the range of 0.5 to 3.0 GPa, the structure, molecular weight, usage amount, etc. of the polyamide resin and / or polyimide resin are not limited.

[0025] From the perspective of reducing the shrinkage amount during curing, etc., the photosensitive resin composition of this 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 denoted as IM and the number of moles of amide groups contained in the polyimide resin is denoted as AM, the imidization rate represented by {IM / (IM + AM)}×100(%) is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. In short, the polyimide resin is preferably a resin having no or few ring-opened 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 the ring-closure reaction does not occur). As a result, it is possible to further improve the reliability of electronic devices and the flatness of the cured film. The imidization rate can be known, for example, from the area of the peak corresponding to the amide group and the area of the peak corresponding to the imide group in the NMR spectrum. As another example, the imidization rate can be known from the area of the peak corresponding to the amide group and the area of the peak corresponding to the imide group in the infrared absorption spectrum.

[0026] The polyamide resin and / or the polyimide resin preferably contains fluorine atoms. As the finding of the present inventors, the polyamide resin and / or the polyimide resin containing fluorine atoms tend to have better solubility in organic solvents than those not containing fluorine atoms. Therefore, by using the polyamide resin and / or the polyimide resin containing fluorine atoms, it is easy to make the properties of the photosensitive resin composition into a varnish state. The amount (mass ratio) of fluorine atoms in the polyamide resin and / or the polyimide resin containing fluorine atoms is, for example, 1 to 30% by mass, preferably 3 to 28% by mass, and more preferably 5 to 25% by mass. By containing a certain amount of fluorine atoms in the resin, it is easy to obtain sufficient solubility in organic solvents. 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 variously designing the terminals of the polyamide resin and / or the polyimide resin, for example, the mechanical properties (such as tensile elongation) of the cured product can be further improved.

[0028] As an example, it is preferable that the polyamide resin and / or the polyimide resin have a group capable of reacting with an epoxy group to form a bond at its terminal. Examples of such a group include an acid anhydride group, a hydroxy group, an amino group, a carboxy group, and the like.

[0029] Preferably, the polyamide resin and / or the polyimide resin have an acid anhydride group at their terminals. In the photosensitive resin composition of the present embodiment, the acid anhydride group and the epoxy group are sufficiently likely to form a bond. The acid anhydride group is preferably a group having an acid anhydride skeleton of a cyclic structure. The "cyclic structure" here is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.

[0030] Supplementary to the terminal structure, it is preferable that the polyamide resin and / or the polyimide resin do not have a maleimide structure at their terminals.

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

[0032]

Chemical formula

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

[0034]

Chemical formula

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

[0036] In general formulas (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 an organic solvent, in general formulas (PA-1) and (PI-1), it is preferable that both X and Y are fluorine atom-containing groups.

[0037] In general formulas (PA-1) and (PI-1), the divalent organic group of X and / or the tetravalent organic group of Y preferably contains an aromatic ring structure, and more preferably contains a benzene ring structure. Thereby, the heat resistance tends to be further enhanced. The benzene ring here may be substituted with a fluorine atom-containing group such as a fluorine atom or a perfluoroalkyl group (preferably a trifluoromethyl group), or may be substituted with other groups. The divalent organic group of X and / or the tetravalent organic group of Y in general formulas (PA-1) and (PI-1) preferably has 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 here include an alkylene group, a perfluoroalkylene group, and an ether group. The alkylene group and the perfluoroalkylene group may be linear or branched. In general formulas (PA-1) and (PI-1), the number of carbon atoms of the divalent organic group of X is, for example, 6 to 30. In general formulas (PA-1) and (PI-1), the number of carbon atoms of the tetravalent organic group of Y is, for example, 6 to 20. Each of the two imide rings in general formula (PI-1) is preferably a 5-membered ring.

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

[0039]

Chemical formula

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

[0041] [Chemical formula]

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

[0043] Specific embodiments of X are the same as those described in general formulas (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, more preferably 1 to 3.

[0044] The polyamide resin can typically be obtained by reacting (condensation polymerizing) a diamine and an acid dianhydride. The polyimide resin can be obtained by imidizing (ring-closing reacting) the polyamide resin. Further, a desired functional group may be introduced at the polymer terminal as needed. For specific reaction conditions, reference can be made to the examples described below and the description in Patent Document 1 mentioned above.

[0045] In the finally obtained polyamide resin and / or polyimide resin, the diamine is incorporated into the polymer as the divalent organic group X in general formula (PA-1) or (PI-1). Further, the acid dianhydride is incorporated into the polymer as the tetravalent organic group Y in general formula (PA-1) or (PI-1). In the synthesis of the polyamide resin and / or polyimide resin, one or more diamines can be used, and one or more acid dianhydrides can also 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, 2,2'-bis(p-aminophenyl)hexafluoropropane, bis(trifluoromethoxy)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-DABTF), 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 acid dianhydride as the raw material include pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenyl sulfone-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), and the like. Of course, the usable acid dianhydrides are not limited to these. One or more acid dianhydrides can be used.

[0048] Basically, the usage ratio of diamine to acid dianhydride is 1:1 in terms of molar ratio. However, in order to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using diamine in excess, the terminals (both terminals) of the polyamide resin and / or polyimide resin are likely to be amino groups. On the other hand, by using acid dianhydride in excess, the terminals (both terminals) of the polyamide resin and / or polyimide resin are likely to be acid anhydride groups. As described above, in this embodiment, it is preferable that the polyamide resin and / or polyimide resin has an acid anhydride group at its terminal. Therefore, in this embodiment, it is preferable to use acid dianhydride in excess during the synthesis of the polyamide resin and / or polyimide resin.

[0049] Some reagent may be reacted with the amino group and / or acid anhydride group at the terminal of the polyamide resin and / or polyimide resin obtained by polycondensation so that the resin terminal 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, more preferably 10,000 to 50,000. When the weight average molecular weight of the polyamide resin and / or polyimide resin is somewhat large, sufficient heat resistance of the cured film can be obtained, for example. Also, when the weight average molecular weight of the polyamide resin and / or polyimide resin is not too large, it becomes easier to dissolve the polyamide resin and / or polyimide resin 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 this embodiment preferably contains a polyfunctional (meth)acrylate compound. As the polyfunctional (meth)acrylate compound, those having two or more (meth)acryloyl groups in one molecule can be mentioned without particular limitation.

[0052] As the finding of the present inventors, by using a polyamide resin and / or polyimide resin and a polyfunctional (meth)acrylate compound in combination, it is easy to design a photosensitive resin composition in which E' 220 is 0.5 to 3.0 GPa, and there is a tendency that the performance of the cured film is more likely to be better.

[0053] Although the details are unknown, when the polyfunctional (meth)acrylate compound cures (polymerizes), it is considered that a structure that "entangles" complexly with the polyamide resin and / or polyimide resin is formed. In particular, the polyfunctional (meth)acrylate compound is presumed to form 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 can have a cyclic skeleton by ring closure of at least a part of the polyamide structure by heat during polymerization. By forming such a complexly entangled structure, it is presumed that E' 220 becomes 0.5 to 3.0 GPa and the performance of the cured film is improved.

[0054] From the perspective of realizing the intertwined structure as described above and from the perspective of obtaining a cured film with high durability and good chemical resistance, the polyfunctional (meth)acrylate compound preferably has 3 or more functional groups. There is no particular upper limit to the number of functional groups of the polyfunctional (meth)acrylate compound, but from the viewpoint of easy availability of raw materials, etc., the upper limit of the number of functional groups is, for example, 11 functional groups. As a general tendency, 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 increase. 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 such as the tensile elongation of the cured film tend to be good.

[0055] As an example, the polyfunctional (meth)acrylate compound preferably contains a (meth)acrylate compound having 7 or more functional groups.

[0056] As an example, the polyfunctional (meth)acrylate compound preferably contains a (meth)acrylate compound having 5 to 6 functional groups.

[0057] As an example, the polyfunctional (meth)acrylate compound preferably contains a (meth)acrylate compound having 3 to 4 functional groups.

[0058] As an example, the polyfunctional (meth)acrylate compound can contain 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. A plurality of R's may be the same or different.

[0059]

Chemical formula

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

[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, epoxy acrylates such as di(meth)acrylate of bisphenol A diglycidyl ether, di(meth)acrylate of hexanediol diglycidyl ether, and urethane (meth)acrylate obtained by the reaction of polyisocyanate and hydroxyl group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate, etc.

[0062] Commercially available products such as Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Biscoat #230, Biscoat #300, Biscoat #802, Biscoat #2500, Biscoat #1000, Biscoat #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.), etc.

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

[0064] When using a polyfunctional (meth)acrylate compound, the amount of the polyfunctional (meth)acrylate compound relative to 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 usage amount of the polyfunctional (meth)acrylate compound is not particularly limited, but by appropriately adjusting the usage amount as described above, one or more of various performances can be further enhanced. As described above, in the photosensitive resin composition of this embodiment, it is considered that a "crosslinked structure" of the polyamide resin and / or polyimide resin and the polyfunctional (meth)acrylate is formed by curing. However, by appropriately adjusting the usage amount of the polyfunctional (meth)acrylate compound with respect to the polyamide resin and / or polyimide resin, it is considered that the polyamide resin and / or polyimide resin and the polyfunctional (meth)acrylate compound are moderately crosslinked, and the amount of extra components not involved in the crosslinking is reduced. And it is considered that the performance is further improved.

[0065] (Photosensitizer) The photosensitive resin composition of this embodiment preferably contains a photosensitizer. The photosensitizer is not particularly limited as long as it can generate active species by light and cure the photosensitive resin composition.

[0066] The photosensitizer preferably contains a photo radical generator. The photo radical generator is particularly effective for polymerizing the polyfunctional (meth)acrylate compound.

[0067] The photo radical generator that can be used is not particularly limited, and known ones can be appropriately used. For example, alkylphenone compounds such as 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 - methylthiophenyl) - 2 - morpholinopropan - 1 - one, 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 benzophenone, 4,4′ - bis(dimethylamino)benzophenone, 2 - carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2 - ethylthioxanthone, 2 - isopropylthioxanthone, 2 - chlorothioxanthone, 2,4 - dimethylthioxanthone, 2,4 - diethylthioxanthone; halomethylated triazine compounds such as 2 - (4 - methoxyphenyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - methoxynaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - ethoxynaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine, 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, 2 - trichloromethyl - 5 - furyl - 1,3,4 - oxadiazole;Imidazole 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, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole; Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acyloxime); Titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; Benzoic acid ester compounds such as p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid; Acridine compounds such as 9-phenylacridine; etc. can be mentioned. Among these, oxime ester compounds can be preferably used.

[0068] When the photosensitive resin composition contains a photosensitizer, it may contain only one kind of photosensitizer or two or more kinds of photosensitizers. When using a photosensitizer, its usage amount is, for example, 1 to 30 parts by mass, 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 this embodiment preferably contains a thermal radical initiator. By using a thermal radical initiator, it is easy to appropriately adjust the value of CTE2 / CTE1 described later, further improve the reliability of the electronic device, and further enhance the heat resistance of the cured film. This is considered to be because the polymerization reaction of the polyfunctional (meth)acrylate compound is further promoted by using a thermal radical initiator.

[0070] The thermal radical initiator preferably contains an organic peroxide. Examples of the organic peroxide include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3 - tetramethylbutyl peroxy 2 - ethylhexanoate, oxalic acid peroxide, 2,5 - dimethyl - 2,5 - bis(2 - ethylhexanoylperoxy)hexane, 1 - cyclohexyl - 1 - methylethyl peroxy 2 - ethylhexanoate, t - hexyl peroxy 2 - ethylhexanoate, t - butyl peroxy 2 - ethylhexanoate, m - toluoyl 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, and the like.

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

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

[0073] As the epoxy resin, compounds having one or more (preferably two or more) epoxy groups in one molecule can be appropriately used. Specific examples of the epoxy resin 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, glycidyl ether of bisphenol A (or F), etc., glycidyl esters such as adipic acid diglycidyl ester, 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, dicyclopentadiene monoxide, bis(2,3-epoxycyclopentyl) ether, alicyclic epoxy resins such as Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Epolide GT401 manufactured by Daicel Corporation, 2,2'-(((((1-(4-(2-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane) (for example, Techmore VG3101L manufactured by Printteck Co., Ltd.), aliphatic polyglycidyl ethers such as Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epil TMP (manufactured by NOF Corporation), 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)tri·siloxane (for example, DMS-E09 (manufactured by Gelest Inc.)), and the like.

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

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

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

[0077] Examples of the curing catalyst include compounds known as curing catalysts (often also called curing accelerators) for epoxy resins. For example, diazabicycloalkenes such as 1,8-diazabicyclo[5,4,0]undecene-7 and their derivatives; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphines such as triphenylphosphine and methyldiphenylphosphine; tetra-substituted phosphonium salts such as tetraphenylphosphonium·tetraphenylborate, tetraphenylphosphonium·tetrabenzoate borate, tetraphenylphosphonium·tetranaphthoic acid borate, tetraphenylphosphonium·tetranaphthoyl oxyborate, tetraphenylphosphonium·tetranaphthyloxyborate, tetraphenylphosphonium·4,4'-sulfonyldiphenolate; triphenylphosphine adducted with benzoquinone, etc. Among them, organic phosphines are preferably mentioned.

[0078] When using a curing catalyst, its amount is, for example, 1 to 80 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass of the epoxy resin.

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

[0080] As the silane coupling agent, for example, an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth)acryloyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a vinyl group-containing silane coupling agent, a ureido group-containing silane coupling agent, a sulfide group-containing silane coupling agent, a silane coupling agent having a cyclic anhydride structure, etc. can be used.

[0081] Examples of the amino group-containing silane coupling agent 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, N-phenyl-γ-amino-propyltrimethoxysilane, etc. Examples of the epoxy group-containing silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, etc. Examples of the (meth)acryloyl group-containing silane coupling agent include γ-((meth)acryloyloxypropyl)trimethoxysilane, γ-((meth)acryloyloxypropyl)methyldimethoxysilane, γ-((meth)acryloyloxypropyl)methyldiethoxysilane, and the like. Examples of the mercapto group-containing silane coupling agent include 3-mercaptopropyltrimethoxysilane and the like. Examples of the vinyl group-containing silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like. Examples of the ureido group-containing silane coupling agent include 3-ureidopropyltriethoxysilane and the like. 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-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, and the like.

[0082] In this embodiment, in particular, a silane coupling agent having a cyclic anhydride structure is preferably used. Although the details are unclear, the cyclic anhydride structure is likely to react with the main chain, side chain, and / or terminal of the polyamide resin and / or polyimide resin, and thus a particularly good effect of improving adhesion is presumed to be obtained.

[0083] When a silane coupling agent is used, it may be used alone, or two or more adhesion aids may be used in combination. When a silane coupling agent is used, its usage amount 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 still more preferably 0.5 to 10 parts by mass when the usage amount of the polyamide resin and / or polyimide resin is 100 parts by mass.

[0084] (Surfactant) The photosensitive resin composition of this embodiment preferably contains a surfactant. Thereby, the coatability of the photosensitive resin composition and the flatness of the film can be further improved. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic-based surfactants.

[0085] The surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. Thereby, in addition to obtaining a uniform resin film (improvement of coatability) and improvement of developability, it also contributes to improvement of adhesion strength. From another viewpoint, the surfactant is preferably nonionic. The use of a nonionic surfactant is preferable, for example, in suppressing an unintentional reaction with other components in the composition and enhancing the storage stability of the composition.

[0086] Examples of commercially available products that can be preferably used as the surfactant include, for example, surfactants having an oligomer structure containing fluorine such as F-251, F-253, F-281, F-430, F-477, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94 of the "Megafac" series manufactured by DIC Corporation, fluorine-containing nonionic surfactants such as Ftergent 250 and Ftergent 251 manufactured by NEOST Co., Ltd., and silicone-based surfactants such as the SILFOAM (registered trademark) series (for example, SD 100 TS, SD 670, SD 850, SD 860, SD 882) manufactured by Wacker Chemie AG. Also, FC4430, FC4432, etc. manufactured by 3M Company can also be mentioned as preferable surfactants.

[0087] When the photosensitive resin composition of the present embodiment contains a surfactant, it can contain one or two or more surfactants. When the photosensitive resin composition of the present embodiment contains a surfactant, its amount is, for example, 0.001 to 1 part by mass, preferably 0.005 to 0.5 part by mass, when the content of the polyamide resin and / or polyimide resin is 100 parts by mass.

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

[0089] When the photosensitive resin composition of the present embodiment contains water, its amount is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, still more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the total solid content (non-volatile component) of the photosensitive resin composition. The water content of the photosensitive resin composition can be quantified by the Karl Fischer method.

[0090] (Properties of solvent / composition) The photosensitive resin composition of the present embodiment preferably contains a solvent. Thereby, a photosensitive resin film can be easily formed on a substrate (especially a substrate having a step) by a coating method. The solvent usually contains an organic solvent. The solvent is not particularly limited as long as it can dissolve or disperse the above-described respective components and does not substantially chemically react with each constituent component.

[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 solvent may be used alone or in combination of two or more.

[0092] When the photosensitive resin composition of the present embodiment contains a solvent, the photosensitive resin composition of the present embodiment is usually in the form of a varnish. 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. Further, since the polyamide resin and / or the polyimide resin is "dissolved" in the solvent, a homogeneous cured film can be obtained.

[0093] When using a solvent, the concentration of the total solid content (non-volatile component) in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 45% by mass. By setting it within this range, each component can be sufficiently dissolved or dispersed. Also, good coatability can be ensured, which in turn leads to an improvement in flatness during spin coating. Furthermore, by adjusting the content of the non-volatile component, the viscosity of the photosensitive resin composition can be appropriately controlled. From another perspective, the proportion of the polyamide resin and / or polyimide resin and the polyfunctional (meth)acrylate compound in the entire composition is preferably 20 to 50% by mass. By using a certain amount of polyamide resin and / or polyimide resin and polyfunctional (meth)acrylate compound, it is easy to form a film with an appropriate thickness.

[0094] (Other components) In addition to the above components, the photosensitive resin composition of this embodiment may contain components other than the above-mentioned components as necessary. Examples of such components include antioxidants, fillers such as silica, sensitizers, film-forming agents, and the like.

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

[0096] From one perspective, since the thermal expansion behavior of the cured product of the photosensitive resin composition of this embodiment is appropriate, the reliability of the electronic device can be further enhanced. Specifically, · Let the glass transition temperature of the cured film obtained by heating the photosensitive resin composition at 170 °C for 2 hours be Tg [°C], · Let the coefficient of thermal expansion of the cured film in the temperature range from Tg - 50 [°C] to Tg - 20 [°C] be CTE1, · Let the coefficient of thermal expansion of the cured film in the temperature range from Tg + 20 [°C] to Tg + 50 [°C] be CTE2. When this is the case, the value of CTE2 / CTE1 is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5. By designing the photosensitive resin composition so that CTE2 does not become excessively larger than CTE1, it is considered that the alteration / softening of the cured film due to heating in the electronic device manufacturing process is further suppressed. And it is considered that the reliability of the electronic device is further improved. The value of CTE2 / CTE1 is preferably close to 1 ideally, but from the perspective of realistic composition design, the lower limit is about 1.1 for example.

[0097] Incidentally, the value of CTE1 itself is preferably 2×10 -5 ~8×10 -5 / °C, more preferably 2×10 -5 ~8×10 -5 / °C, even more preferably 3×10 -5 ~7×10 -5 / °C, particularly preferably 4×10 -5 ~6×10 -5 / °C. Also, the value of CTE2 itself is preferably 2×10 -5 ~100×10 -5 / °C, more preferably 2×10 -5 ~80×10 -5 / °C, even more preferably 5×10 -5 ~60×10 -5 / °C, particularly preferably 5×10 -5 ~50×10 -5 / °C. Also, the glass transition temperature Tg is preferably 170 - 270°C, more preferably 170 - 250°C, even more preferably 200 - 250°C, particularly preferably 210 - 230°C.

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

[0099] The storage modulus E' at 250°C of the cured film of the photosensitive resin composition of this embodiment in the dynamic viscoelasticity measurement under the aforementioned [conditions] 250 is preferably 0.3 GPa or more, more preferably 0.3 GPa or more and 3.0 GPa or less, even more preferably 0.5 GPa or more and 2.0 GPa or less. The storage modulus E' at 280°C of the cured film of the photosensitive resin composition of this embodiment in the dynamic viscoelasticity measurement under the aforementioned [conditions] 280is preferably 0.1 GPa or more, more preferably 0.1 GPa or more and 2.0 GPa or less, and still more preferably 0.2 GPa or more and 1.0 GPa or less. E' 250 and E' 280 By designing the photosensitive resin composition so that E' and the like are within the above numerical range, for example, peeling of the cured film can be suppressed even in a reflow process that requires high temperature, and it is considered that the reliability of the electronic device can be further improved.

[0100] <Method for manufacturing an electronic device, electronic device> The method for manufacturing an electronic device according to this embodiment is a film forming step of forming a photosensitive resin film on a substrate using the above-described photosensitive resin composition, an exposure step of exposing the photosensitive resin film, a development step of developing the exposed photosensitive resin film, and includes Further, the method for manufacturing an electronic device according to this embodiment preferably includes a thermal curing step of heating and curing the exposed photosensitive resin film after the above-described development step. Thereby, a cured film with sufficient heat resistance can be obtained. As described above, an electronic device including a cured film of the photosensitive resin composition according to this embodiment can be manufactured.

[0101] The film forming step is usually performed by applying a photosensitive resin composition on a substrate. The film forming step can be performed 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. The heating at this time is performed, for example, by heating at a temperature of 80 to 150°C for 1 to 60 minutes. The thickness of the dried photosensitive resin film appropriately varies depending on the structure of the electronic device finally to be obtained, but is, for example, about 1 to 100 μm, specifically about 1 to 50 μm.

[0102] The exposure amount in the exposure step is not particularly limited. 100 to 2000 mJ / cm2 is preferred, and 200 to 1000 mJ / cm 2 is more preferred. The light source used for exposure is not particularly limited, and any light source that emits light with a wavelength at which the photosensitizer in the photosensitive resin composition reacts (for example, g-line or i-line) may be used. 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. Preferably, it is 50 to 150°C, more preferably 50 to 130°C, still more preferably 55 to 120°C, and particularly preferably 60 to 110°C. Also, the time for post-exposure baking is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, still more preferably 1 to 15 minutes. In the exposure step, a photomask can be used. Thereby, a desired "pattern" can be formed using the photosensitive resin composition.

[0103] Examples of the developer include organic developers, water-soluble developers, etc. In the present embodiment, the developer preferably contains an organic solvent. More specifically, the developer is preferably a developer mainly composed of an organic solvent (a developer in which 95 mass% or more of the components is an organic solvent). By developing with a developer containing an organic solvent, it becomes possible to suppress the swelling of the pattern by the developer more than when developing with an alkaline developer (aqueous system). That is, it is easier to obtain a finer pattern.

[0104] Specific examples of the organic solvent that can be used in the developer include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, ether solvents such as propylene glycol monomethyl ether, and the like. As the developer, an organic solvent developer consisting only of an organic solvent and containing no components other than unavoidably contained impurities may be used. Unavoidably contained impurities include metal elements and moisture, but there is no better situation than having few unavoidably contained impurities from the viewpoint of preventing contamination of electronic devices.

[0105] The method of bringing the developer into contact with the photosensitive resin layer 2510 is not particularly limited. Commonly known methods such as the dipping method, paddle method, spray method, etc. can be appropriately applied.

[0106] The time of the development process is usually in the range of about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the film thickness of the resin film, the shape of the pattern to be formed, etc.

[0107] The conditions of the thermosetting process are not particularly limited, but for example, the heating temperature can be about 160 to 250 °C and the time can be about 30 to 240 minutes.

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

[0109] First, as shown in Fig. 1(a), a structure is prepared in which a plurality of semiconductor chips 40 obtained by dicing a semiconductor wafer preliminarily passivated by forming a passivation film 50 are arranged at a predetermined interval, and the terminal surface (the surface on the side where the electrode pads 30 are arranged) of the semiconductor chip 40 is attached to the adhesive surface of the adhesive member 200. As the 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), it is preferable that the plurality of semiconductor chips 40 are embedded inside the encapsulant 10 such that the electrode pads 30 provided on the respective surfaces of the plurality of semiconductor chips 40 all face the same direction. On the electrode pads 30 provided on the semiconductor chip 40, a pillar-shaped conductor portion made of a metal such as copper may be formed. Further, a solder bump may be formed on the end face of the conductor portion opposite to the side where the electrode pad is arranged.

[0110] Next, as shown in FIG. 1(b), a plurality of semiconductor chips 40 attached to the adhesive member 200 are covered and sealed with a cured product of a semiconductor encapsulating resin composition. In the present embodiment, the cured product of the semiconductor encapsulating resin composition indicates a sealing material. As such a semiconductor encapsulating resin composition, known materials 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 the method for sealing the semiconductor chip 40 using the semiconductor encapsulating resin composition include a transfer molding method, a compression molding method, an injection molding method, and a lamination method. Among them, from the viewpoint of forming the sealing material 10 without leaving an unfilled portion, the transfer molding method, the compression molding method, or the lamination method is preferable. Therefore, the semiconductor encapsulating resin composition used in this manufacturing method is preferably in the form of granules, powder granules, tablets, or sheets. Further, from the viewpoint of suppressing the occurrence of displacement of the semiconductor chip 40 during the molding of the sealing material 10, the compression molding method is particularly preferable.

[0112] Next, as shown in FIG. 1(c), the adhesive member 200 is peeled off. By doing so, a structure in which a plurality of semiconductor chips 40 having electrode pads 30 on the surface are embedded inside the sealing material 10 can be obtained. The adhesive member 200 is preferably peeled off from the structure after reducing the adhesion between the adhesive member 200 and the structure. Specifically, a method of reducing the adhesion by deteriorating the adhesive layer of the adhesive member 200 forming the adhesion site, for example, by performing ultraviolet irradiation or heat treatment on the adhesion site between the adhesive member 200 and the structure, can be mentioned. The adhesive member 200 is not particularly limited as long as it adheres to the semiconductor chip 40, and examples thereof include a member in which a back grind tape and an adhesive layer are laminated. The structure shown in FIG. 1(c) relates to a mode in which the surface of the semiconductor chip 40 on the side opposite to the side where the electrode pads 30 are arranged is covered with the sealing material 10. However, in this manufacturing method, before peeling the adhesive member 200, there may be a step of polishing and removing the sealing material 10 by a known method so that the surface of the semiconductor chip 40 on the side opposite to the side where the electrode pads 30 are arranged is exposed.

[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-described structure on the side where the electrode pads 30 are embedded and 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 the method for applying the resin composition, known methods such as a spin coating method, a slit coating method, and an inkjet method can be adopted. Among them, it is preferable to adopt the spin coating method.

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

[0115] In this manufacturing method, before forming the first insulating resin film 60, it is preferable to perform plasma treatment on the surface of the sealing material 10 on the side where the first insulating resin film 60 is to be formed. By doing so, the wettability of the first insulating resin film 60 can be improved. As a result, the adhesion between the sealing material 10 and the first insulating resin film 60 can be made even better. In the plasma treatment, for example, as the treatment gas, argon gas, an oxidizing gas, or a fluorine-based gas can be used. As the oxidizing gas, O 2 gas, O 3 gas, CO gas, CO 2 gas, NO gas, NO 2Examples include gas. As the processing gas, for example, an oxidizing gas is preferably used. Further, as the oxidizing gas, for example, O 2 gas is preferably used. Thereby, a specific functional group can 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. In addition to the ashing treatment, a treatment of contacting with plasma derived from an inert gas may be performed. Further, the plasma treatment according to the present manufacturing method is preferably a plasma treatment performed without applying a bias voltage to the treatment target or a plasma treatment performed using a non-reactive gas. In addition, in the present manufacturing method, a chemical solution treatment may be performed instead of the plasma treatment, or both the plasma treatment and the chemical solution treatment may be performed. Examples of the chemical agent that can be used for the chemical solution treatment include alkaline permanganate aqueous solutions such as potassium permanganate and sodium permanganate.

[0117] Next, as shown in FIG. 2(b), a first opening 250 for exposing a part of the electrode pad 30 is formed in the first insulating resin film 60. As a method for forming the first opening 250, a photolithography method or a laser processing method can be used. Further, for the formed first opening 250, it is preferable to perform a descum treatment for removing scum (resin residue) generated when forming the first opening 250.

[0118] The descum treatment may be performed by plasma irradiation. At this time, as the processing gas, for example, argon gas, O 2 gas, O 3 gas, CO gas, CO 2 gas, NO gas, NO 2 gas or a fluorine-based gas can be used.

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

[0120] As the plating method, for example, an electrolytic plating method or an electroless plating method can be adopted. When the electroless plating method is used, the conductive film 110 can be formed as follows. Hereinafter, an example of forming a conductive film 110 composed of two layers of nickel and gold will be described, but it is not limited thereto. First, a nickel plating film is formed. When performing electroless nickel plating, the structure shown in FIG. 2(b) is immersed in the plating solution. By doing so, the conductive film 110 can be formed on the electrode pad 30 and the surface of the first insulating resin film 60. The plating solution can use, for example, nickel salts and hypophosphite as a reducing agent. Subsequently, electroless gold plating is performed on the nickel plating film. The method of electroless gold plating is not particularly limited, but for example, it can be performed by displacement gold plating performed by substitution of gold ions and ions of the underlying metal.

[0121] Thus, in FO-WLP, the semiconductor chip 40 is embedded by 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. In the region of the encapsulant 10 that embeds the semiconductor chip 40, a conductive film 110 (redistribution layer) connected to the electrode pads 30 of the semiconductor chip 40 is also provided, and the bump is electrically connected to the electrode pads 30 of the semiconductor chip 40 via the conductive film 110 (redistribution 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. Then, in the present embodiment, as shown in Fig. 3(b), a second opening 300 for exposing a part of the conductive film 110 is formed. As the method for forming the second insulating resin film 70 and the second opening 300, the same method as the method for forming the first insulating resin film 60 and the first opening 250 can be used. Also, as the material for forming the second insulating resin film 70, the photosensitive resin composition used for forming the first insulating resin film 60 (that is, the composition described in the <photosensitive resin composition> section) can be used.

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

[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 a plurality of 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 including four conductive films (wiring layers) and five insulating resin films can also be manufactured. In this case, the same method as the method for forming the conductive film 110 can be used as the method for forming the conductive film (wiring layer). Also, the same method as the method for forming the first insulating resin film 60 can be used as the method for forming the insulating resin film. Even when manufacturing an electronic device having the above-described multilayer wiring structure, in the same manner as the above-described method, by melting the end portion of the solder bump 80 or the bonding wire on the outermost layer and fusing it to the conductive film (wiring layer), the obtained electronic device can be electrically connected.

[0125] This manufacturing method relates to a technique of forming an insulating resin film and a conductive film (wiring layer) only on one surface of a structure starting from the structure shown in Fig. 1(c). However, when the surface of the structure shown in Fig. 1(c) opposite to the side where the electrode pad 30 in the semiconductor chip 40 is arranged is also exposed, an insulating resin film may be formed on both surfaces of the structure.

[0126] This manufacturing method can also be applied to a process for manufacturing a semiconductor package with a chip size. However, from the viewpoint of improving the productivity of the semiconductor package, it may be applied to a process for manufacturing a so-called wafer-level package or a process for manufacturing a panel-level package on the premise of using a large-area panel larger than the wafer size.

[0127] As described above, the embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than the above can be adopted. Also, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the range that can achieve the object of the present invention are included in the present invention.

Example

[0128] Embodiments of the present invention will be described in detail based on examples and comparative examples. Just to be clear, the present invention is not limited only to the examples. Hereinafter, "DMAc" is an abbreviation for dimethylacetamide. Other abbreviations will be appropriately explained in the text.

[0129] <Synthesis of Polymer> (Synthesis of Polymer (A-1)) Into a 3 L glass separable flask equipped with a stirrer and a stirring blade, 64.1 g (0.20 mol) of TFMB <2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl>, 97.7 g (0.22 mol) of 6FDA <4,4'-(hexafluoroisopropylidene)diphthalic anhydride> and 500 g of DMAc were charged and stirred to dissolve TFMB and 6FDA in DMAc. Further, under a nitrogen stream, stirring was continued at room temperature for 12 hours to carry out a polymerization reaction to obtain 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. Then, the liquid temperature was further maintained at 20 to 100 °C and stirring was continued for 24 hours to carry out an imidization reaction to obtain a polyimide solution.

[0131] The obtained polyimide solution was poured into 1,000 g of methanol with stirring in a container having a volume of 5 L to precipitate a polyimide resin. Then, the solid polyimide resin was filtered off using a suction filtration device, and further washed with 1,000 g of methanol. Then, drying was carried out at 100 °C for 24 hours using a vacuum dryer, and further dried at 200 °C for 3 hours. Thus, a polymer (A-1), which is a polyimide powder having an acid anhydride group at the terminal, was obtained. The weight average molecular weight (Mw) of polymer (A-1) by GPC measurement was 25,000. Also, polymer (A-1) was 1 measured by 1H-NMR, and the imidization rate (definition is as described above) was calculated from the quantitative value of the amide peak with respect 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 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. And a polyimide powder (Polymer (A-2)) having an acid anhydride group at the terminal was obtained. The weight average molecular weight (Mw) of Polymer (A-2) by GPC measurement was 26,000. Also, the imidization rate of Polymer (A-2) by NMR measurement was 99% or more.

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

[0134] (Synthesis of Polymer (A-4)) Polymer synthesis was carried out in the same manner as 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. And a polyimide resin (A-4) having an acid anhydride group at the terminal was obtained. The weight average molecular weight (Mw) of Polymer (A-4) by GPC measurement was 24,000. Also, the imidization rate of Polymer (A-4) by NMR measurement was 99% or more.

[0135] (Synthesis of Polymer (A-5)) A polymer was synthesized in the same manner as polymer (A-1), except that 85.7 g (0.20 mol) of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene was used instead of 0.20 mol of TFMB64.1g. And a 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 polymer (A-5) by GPC measurement was 25,000. Also, the imidization rate of polymer (A-5) by NMR measurement was 99% or more.

[0136] <Preparation of photosensitive resin composition> Each raw material compounded according to Table 1 shown below was stirred at room temperature until the raw materials were completely dissolved to obtain a solution. Then, the solution was 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 of each component in Table 1 are as follows.

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

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

[0140] [Chemical formula]

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

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

[0143] [Chemical formula]

[0144] <Photosensitizer> (C-1) Irugacure OXE01 (manufactured by BASF, an oxime ester type photo radical generator) (C-2) Adeka Arcles NCI-730 (manufactured by ADEKA Corporation, an oxime ester type photo radical generator)

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

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

[0147] <Curing catalyst> (F-1) Tetraphenylphosphonium 4,4'-sulfonyldiphenolate The synthesis method of the above curing catalyst (F-1) is as follows. Into a separable flask equipped with a stirring device, 37.5 g (0.15 mol) of 4,4'-bisphenol S and 100 mL of methanol were charged, stirred and dissolved at room temperature. While continuing stirring, a solution prepared by dissolving 4.0 g (0.1 mol) of sodium hydroxide in 50 mL of methanol in advance was added. Subsequently, a solution prepared by dissolving 41.9 g (0.1 mol) of tetraphenylphosphonium bromide in 150 mL of methanol in advance was added. Stirring was continued for a while, and after adding 300 mL of methanol, the solution in the flask was added dropwise with stirring into a large amount of water to obtain a white precipitate. The precipitate was filtered and dried. Thus, the target product as white crystals was obtained.

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

[0149] <Surfactant> (H-1) FC4432 (manufactured by 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. measurement)> (Preparation of test piece) The photosensitive resin composition was spin-coated on 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 coated film. The obtained coated film was exposed with a high-pressure mercury lamp at 1000 mJ / cm 2 . Then, post-exposure baking was carried out at 120°C for 3 minutes, followed by immersion in cyclopentanone for 30 seconds. Furthermore, after that, it was heat-treated at 170°C for 2 hours under a nitrogen atmosphere to obtain a cured film of the photosensitive resin composition. The obtained cured product, together with the silicon wafer, was cut with a dicing saw to a width of 5 mm. The cured film was peeled off from the wafer by immersing the cut product in an aqueous hydrofluoric acid solution of 2 mass%. The peeled cured film was dried at 60 °C for 10 hours to obtain test pieces (30 mm × 5 mm × 10 μm thick).

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

[0153] <Measurement of Coefficient of Thermal Expansion and Glass Transition Temperature (Tg)> Using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., TMA / SS6000), the test pieces obtained in the same manner as the dynamic viscoelasticity measurement of the above cured film were heated to 300 °C at a heating rate of 10 °C / min. The relationship between temperature and displacement amount at this time was graphed. From the position of the inflection point of the obtained graph, the glass transition temperature (Tg) of the cured product was determined. Also, in the obtained graph, the linear expansion coefficient in the region from Tg - 50 [°C] to Tg - 20 [°C] was defined as CTE1, and the linear expansion coefficient in the region from Tg + 20 [°C] to Tg + 50 [°C] was defined as CTE2, and the value of CTE2 / CTE1 was calculated.

[0154] <Reliability Evaluation (Temperature Cycle Test)> (Preparation of Substrate for Reliability Evaluation) The photosensitive resin composition was spin-coated on 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 coated film. The obtained coated film was irradiated with a high-pressure mercury lamp at 1000 mJ / cm 2Exposure was performed. Subsequently, post-exposure baking was carried out at 120°C for 3 minutes, and then it was immersed in cyclopentanone for 30 seconds. Further, thereafter, it was heated at 170°C for 2 hours under a nitrogen atmosphere for curing treatment. Thus, a cured film of the first-layer photosensitive resin composition was obtained. On the obtained cured film, Ti and Cu were deposited by sputtering at thicknesses of 500 Å and 3000 Å, respectively. Thereafter, Cu wiring was formed to a height of 5 μm by an electrolytic plating method through a resist. After peeling the resist layer, sputtered Cu and sputtered Ti were etched to form Cu wiring with a line / space = 2 μm / 2 μm. Subsequently, the photosensitive resin composition was treated in the same manner as the first layer except that the film thickness was changed to 10 μm, and a substrate for reliability evaluation was obtained.

[0155] (Reliability Test) The substrate for reliability evaluation obtained as described above was set in a temperature cycle test apparatus (TCT apparatus), and heating from -60°C to 200°C and subsequent cooling to -60°C were taken as one cycle, and 1000 cycles of treatment were performed. Subsequently, by FIB (focused ion beam) treatment, a cross-section of the Cu wiring portion was taken and observed by SEM. In each example and comparative example, a total of 10 interfaces between the wiring and the resin film were observed. When peeling was not observed at all in all 10 locations, it was evaluated as ◎ (very good), when peeling was observed at 1 or 2 locations out of 10, it was evaluated as ○ (good), and when peeling was observed at 3 or more locations, it was evaluated as × (bad).

[0156] <Evaluation of Insulation Reliability> (Fabrication of Samples for Insulation Reliability) A Cu wiring substrate was fabricated on which comb-shaped Cu wiring with a width of 5 μm / pitch of 5 μm and a height of 5 μm was formed on a silicon wafer with an oxide film. The photosensitive resin composition was applied onto the above Cu wiring substrate by spin coating so that the film thickness after drying (the thickness of the portion without wiring) was 10 μm, and dried at 120°C for 3 minutes to form a photosensitive resin film. To the obtained photosensitive resin film, using a high-pressure mercury lamp, 300 mJ / cm2 Exposure was carried out. Then, it was immersed in cyclopentanone for 30 seconds. Thereafter, heat treatment was performed at 170 °C for 2 hours under a nitrogen atmosphere to obtain a cured film. This was used as a sample for evaluating insulation reliability.

[0157] (Evaluation of insulation reliability) An evaluation-simulated electronic device was fabricated by soldering the end portion (Cu electrode) of the Cu wiring of the substrate fabricated in the above (Fabrication of sample for insulation reliability) to the electrode wiring. This was placed in an environment of 130 °C / 85% RH while applying a bias of 3.5 V using a B-HAST device. The insulation resistance value between the Cu wirings of the Cu wiring substrate was automatically measured at 6-minute intervals, and when the insulation resistance value became 1.0 × 104 Ω or less, it was regarded as insulation breakdown. Then, the time from the start of the test to insulation breakdown was measured. In the table shown later, when this time was 210 hours or more, it was described as ◎ (very good), when it was from 50 hours to 210 hours, it was described as ○ (good), and when it was less than 50 hours, it was described as × (bad).

[0158] (Evaluation of shear strength at 250 °C) In the same manner as in the above <Evaluation of patterning property>, a remaining pattern of 100 μm × 100 μm was created on an 8-inch silicon wafer on which plated copper was formed. Thereafter, curing treatment was performed at 170 °C for 2 hours under a nitrogen atmosphere to obtain a sample for measuring shear strength. Regarding the obtained sample, using a die shear device (manufactured by Nordson Corporation, Dage-4000), the shear strength (hot shear strength, unit: MPa) at 250 °C was measured under the conditions of a shear rate of 200 nm / second and a shear height of 1 μm. A large value of this means that the cured film is difficult to peel even when exposed to high temperature. That is, from the viewpoint of the reliability of the electronic device, a larger value is preferable.

[0159] (Evaluation of curing shrinkage rate) The photosensitive resin composition was spin-coated on an 8-inch silicon wafer so that the film thickness after drying would be 10 μm. Subsequently, heating was performed at 120 °C for 3 minutes to obtain a photosensitive resin film. The obtained photosensitive resin film was exposed with a high-pressure mercury lamp at 300 mJ / cm2. Then, it was immersed in cyclopentanone for 30 seconds and dried by spin drying to obtain a developed film of the photosensitive resin composition. The film thickness of this developed film was measured and designated as film thickness A. Subsequently, the developed film was cured by heat treatment at 170 °C for 2 hours under a nitrogen atmosphere. Thus, a cured film of the photosensitive resin composition was obtained. The film thickness of this cured film was measured and designated as film thickness B. The film thickness A and film thickness B were substituted into the following formula to calculate the curing shrinkage rate. The curing shrinkage rate is preferably small in order to maintain the flatness after coating on the wiring. Curing shrinkage rate [%] = {(film thickness A - film thickness B) / film thickness A} × 100

[0160] <Evaluation of flatness during coating (step filling flatness)> A Cu wiring substrate with Cu wirings having a width of 5 μm / pitch of 5 μm and a height of 5 μm was fabricated on a silicon wafer with an oxide film. The photosensitive resin composition was coated on this Cu wiring substrate by spin coating so that the film thickness after drying would be 10 μm, and dried at 120 °C for 3 minutes to form a photosensitive resin film. The obtained photosensitive resin film was exposed with a high-pressure mercury lamp at 300 mJ / cm 2 2. Then, it was immersed in cyclopentanone for 30 seconds. Subsequently, it was heat-treated at 170 °C for 2 hours under a nitrogen atmosphere to form a cured film on the substrate. The substrate with the obtained cured film was cut, and its cross-section was polished. The unevenness of the surface of the photosensitive resin film was evaluated by cross-sectional SEM observation. Those with surface unevenness of 1 μm or less were rated as ○ (good), those with surface unevenness of 1 - 3 μm were rated as △ (usable level), and those exceeding 3 μm were rated as × (bad).

[0161] <Evaluation of tensile elongation rate> First, test pieces were prepared in the same manner as in (Preparation of test pieces) of the above <Measurement of dynamic viscoelasticity of cured film (measurement of E' 220 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' 220As a result of the temperature cycle test (wherein the pressure is 0.5 to 3.0 GPa), the evaluation result of insulation reliability, and the shear strength at 250°C were all good. From these evaluation results, it was shown 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. In addition, the cured shrinkage rate of the cured products of the photosensitive resin compositions of Examples 1 to 14 was small, and the evaluation of the step coverage flatness was good. Furthermore, the cured products of the photosensitive resin compositions of Examples 1 to 14 were moderately stretchable. In addition, the photosensitive resin compositions of Examples 1 to 14 had sufficient patterning performance during the manufacture of electronic devices.

[0166] Looking more closely at the examples, the following can be understood. · From the comparison between Example 11 and the other examples, by using a thermal radical generator, the glass transition temperature of the cured product tends to increase, and CTE2 / CTE1 tends to decrease. And by using a thermal radical generator, the reliability tends to improve. This is presumably because the polymerization of the polyfunctional (meth)acrylate compound is further promoted by the use of the thermal radical generator. · From the comparison between Examples 12 and 13 and the other examples, by using an epoxy resin and its curing catalyst, the tensile elongation rate tends to improve. Presumably, a cured film that is more stretchable and less likely to break is formed by the formation (crosslinking) of a bond between the polyamide resin and / or polyimide resin and the epoxy resin. · From the comparison between Example 14 and the other examples, it is considered that the adhesion aid presumably works well due to the presence of water, and the adhesion is improved.

[0167] On the other hand, E' 220 The evaluation results of the photosensitive resin composition of Comparative Example 1 where E' is less than 0.50 GPa were inferior to the evaluation results of the photosensitive resin compositions of Examples 1 to 14.

Explanation of Reference Numerals

[0168] 10 Encapsulant 30 Electrode pad 40 Semiconductor chip 50 Passivation film 60 Insulating resin film (first insulating resin film) 70 Insulating resin film (second insulating resin film) 80 Solder bump 100 Electronic device 110 Conductive film 200 Adhesive member 250 Opening (first opening) 300 Opening (second opening)

Claims

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 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 polyfunctional (meth)acrylate compound.

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

6. 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 claims 1 to 6, The photosensitive resin composition further comprises a thermal radical initiator.

8. The photosensitive resin composition according to any one of claims 1 to 7, The photosensitive resin composition further comprises an epoxy resin.

9. 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 claims 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 claims 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. 12. A method for producing an electronic device according to claim 11, comprising the steps of: A method for manufacturing 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 claims 1 to 10.

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