Photosensitive resin composition, cured product thereof, and wiring structure containing the cured product thereof

Abstract

The present invention provides a photosensitive resin composition, a cured product thereof, and a wiring structure, an electronic component, a semiconductor device, and a camera module containing the cured product thereof. The photosensitive resin composition is not cured by heat treatment at a high temperature, but is cured by irradiation with active energy rays. In the photosensitive resin composition, film reduction after the development process is suppressed. Furthermore, fine patterns can be accurately formed by photolithography. One aspect of the present invention relates to a photosensitive resin composition, a cured product thereof, and a wiring structure, an electronic component, a semiconductor device, and a camera module containing the cured product thereof, wherein the photosensitive resin composition comprises components (A) to (C): (A) a modified polyphenylene ether represented by formula (1) and formula (2), (B) a silsesquioxane compound represented by formula (3), and (C) a photopolymerization initiator.

Description

Technical Field

[0001] One aspect of the present disclosure relates to a photosensitive resin composition, a cured product thereof, and a wiring structure, an electronic component, a semiconductor device, and a camera module containing the cured product thereof. Background Art

[0002] The wiring in the wiring structure constituting electronic components such as integrated circuits has been significantly miniaturized. The spacing between the external terminals for connecting the semiconductor chip contained in the wiring structure to the external wiring has also become extremely narrow. It is difficult to reduce the spacing between the external terminals to below a certain level. Therefore, a rewiring layer such as copper is configured on the surface of the semiconductor chip, and external terminals such as bumps are configured on the rewiring layer. In this way, a specific spacing between the external terminals is maintained. An insulating film made of an insulating material is formed between the surface of the semiconductor chip and the rewiring layer, and between the rewiring layer and the UBM (Under Bump Metallurgy) layer configured with the bumps. As a method for forming an insulating layer for configuring the rewiring layer, a method of patterning by photolithography is adopted. As an insulating material for forming the insulating layer of the wiring structure, a photosensitive resin composition is used.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition for photospacers, the photosensitive resin composition comprising a polymerizable compound, an adhesive, and a photopolymerization initiator. The polymerizable compound has a group containing a bridged ring structure and a group containing an ethylenically unsaturated bond. Patent Document 2 discloses a coating composition configured on an optical fiber or an optical slab waveguide. The coating composition contains a silsesquioxane component, the silsesquioxane component having one or more reactive functional groups that can be cured using ultraviolet irradiation. Patent Document 3 discloses a multilayer body comprising a rewiring layer containing copper, an insulating layer containing polyimide or polybenzoxazole, and a copper oxide layer. Patent Document 4 discloses a photosensitive resin material comprising an alkali-soluble resin, a photosensitizer, and a carboximide compound composed of a molecular structure having a dicarboximide structure to improve adhesion to the rewiring metal.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-128487

[0007] Patent Document 2: Japanese Patent Application No. 2017-534693

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 2017-92152

[0009] Patent Document 4: Japanese Patent Application Laid-Open No. 2017-111383 Summary of the Invention

[0010] Technical problem to be solved by the invention

[0011] However, the photosensitive resin compositions disclosed in Patent Documents 1 to 4 are not cured only by active energy rays (such as ultraviolet rays). In order to cure these photosensitive resin compositions, it is necessary to perform heat treatment at a temperature of about 150°C to 300°C. However, when heat treatment is performed after patterning by photolithography, the formed pattern will be deformed due to the shrinkage caused by heat. Therefore, it is difficult to form the desired fine and precise pattern. For the wiring of the increasingly fine rewiring layer, the line and space (hereinafter also referred to as "L / S") are required to be 2μm / 2μm or less. When L / S is reduced, the pattern deformation caused by heat treatment becomes a big problem. The materials used in the wiring structure need to suppress not only the deformation of the pattern, but also the reduction of the film in the development process after patterning. In addition, electronic components also require high-speed transmission of signals, and the high-frequency transmission of signals is also developing significantly. Therefore, the materials used in the wiring structure of electronic components also need to have excellent electrical properties (low dielectric constant (ε), low dielectric loss tangent (tanδ)) in the high-frequency range, specifically in the frequency range of 1GHz to 10GHz.

[0012] Therefore, one object of the present disclosure is to provide the following photosensitive resin composition, its cured product, and a wiring structure, electronic component, semiconductor device, and camera module containing the cured product. This photosensitive resin composition is cured by irradiation with active energy rays, rather than by high-temperature heat treatment at, for example, 150°C or higher. This photosensitive resin composition suppresses film reduction even after a development step. Furthermore, it enables precise formation of fine patterns using photolithography.

[0013] Technical means to solve technical problems

[0014] Means for solving the above technical problems are as follows, and the present disclosure includes the following aspects.

[0015] [1] A photosensitive resin composition comprising the following components (A) to (C):

[0016] (A) A modified polyphenylene ether resin represented by the following formula (1):

[0017] [Chemistry 1]

[0018]

[0019] Where R 1 ~R 3each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group,

[0020] X represents a q-valent unsubstituted or substituted aromatic hydrocarbon group,

[0021] Y represents an unsubstituted or substituted phenol repeating unit represented by the following formula (2):

[0022] [Chemistry 2]

[0023]

[0024] Where R 4 ~R 7 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkenylcarbonyl group; m represents an integer from 1 to 100,

[0025] n represents an integer from 1 to 6,

[0026] q represents an integer from 1 to 4.

[0027] (B) a compound represented by the following formula (3):

[0028] [Chemistry 3]

[0029]

[0030] as well as,

[0031] (C) Photopolymerization initiator.

[0032] [2] The photosensitive resin composition according to [1], further comprising (D) a bifunctional acrylic resin represented by the following formula (4):

[0033] [Chemistry 4]

[0034]

[0035] In the formula, each R a independently represents a hydrogen atom or a methyl group,

[0036] Each R b independently represent a divalent hydrocarbon group,

[0037] x and y each independently represent an integer of 1 to 5.

[0038] [3] The photosensitive resin composition according to [1] or [2], wherein the component (C) is at least one selected from the group consisting of acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and alkylphenone-based photopolymerization initiators.

[0039] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the mass ratio of the component (A) relative to the total amount of the component (A) and the component (B) is 0.10 to 0.99.

[0040] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of the component (C) is 1.0% by mass to 20.0% by mass relative to 100% by mass of the photosensitive resin composition.

[0041] [6] The photosensitive resin composition according to any one of [2] to [5], wherein the mass ratio of the component (D) relative to the total amount of the component (B) and the component (D) is 0.01 to 0.99.

[0042] [7] The photosensitive resin composition according to any one of [1] to [6], further comprising (E) a crystalline or amorphous thermoplastic resin, but the thermoplastic resin does not include a bifunctional acrylic resin.

[0043] [8] The photosensitive resin composition according to [7], wherein the component (E) is at least one selected from the group consisting of liquid crystal polymer, polyethylene, polypropylene, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyetherketone, polytetrafluoroethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, acrylonitrile-butadiene-styrene, polycarbonate, polyethersulfone, polyetherimide and polyamideimide.

[0044] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the photosensitive resin composition is used to form a wiring structure including a rewiring layer.

[0045]

[10] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [9].

[0046]

[11] A wiring structure comprising the cured product described in

[10] .

[0047]

[12] An electronic component comprising the cured product according to

[10] .

[0048]

[13] A semiconductor device comprising the cured product described in

[10] .

[0049]

[14] A camera module comprising the cured product described in

[10] .

[0050] Beneficial effects

[0051] According to the above aspects of the present disclosure, the following photosensitive resin composition, a cured product obtained by curing the composition, and a wiring structure, electronic component, semiconductor device, and camera module containing the cured product can be provided. This photosensitive resin composition is cured by irradiation with active energy rays, rather than by high-temperature heat treatment at, for example, 150°C or higher. This photosensitive resin composition suppresses film reduction even after development by photolithography. Furthermore, it enables precise formation of fine patterns. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] [ Figure 1 ] is an enlarged view of an example of a three-line pattern with L / S of 2 μm / 2 μm.

[0053] [ Figure 2 ] represents a comparison curve and an ideal comparison curve showing the relationship between the film thickness ratio and the irradiation dose of each cured product obtained using the photosensitive resin compositions of Example 6, Example 7 and Example 12.

[0054] [ Figure 3 ] shows a comparison curve obtained using the photosensitive resin composition of Comparative Example 1, showing the relationship between the film thickness ratio and the irradiation dose of each cured product, and an ideal comparison curve. DETAILED DESCRIPTION

[0055] The following describes embodiments of a photosensitive resin composition according to one aspect of the present disclosure, a cured product obtained by curing the composition, a wiring structure containing the cured product, an electronic component, a semiconductor device, and a camera module. However, the embodiments described below are merely examples embodying the technical concepts of the present disclosure. The technical concepts of the present disclosure are not limited to the photosensitive resin composition described below, a cured product obtained by curing the composition, a wiring structure containing the cured product, an electronic component, a semiconductor device, and a camera module containing the cured product.

[0056] The photosensitive resin composition described in the first embodiment of the present disclosure contains (A) a specific modified polyphenylene ether represented by formula (1) and formula (2) (hereinafter sometimes referred to as "component (A)"), (B) a compound represented by formula (3) (hereinafter sometimes referred to as "component (B)"), and (C) a photopolymerization initiator (hereinafter sometimes referred to as "component (C)"). The photosensitive resin composition contains component (A) modified polyphenylene ether. Therefore, the relative dielectric constant (ε) of the photosensitive resin composition is 3.0 or less, and the dielectric loss tangent (tanδ) is 0.01 or less. The photosensitive resin composition has such a low dielectric constant and low dielectric loss tangent. Therefore, by using the photosensitive resin composition, a cured product with good electrical properties when used in a high frequency range can be obtained. The photosensitive resin composition does not need to be subjected to a high-temperature heat treatment of, for example, 150°C or more in order to obtain a cured product. Therefore, in the cured product obtained by curing the photosensitive resin composition, it is not easy to deform due to shrinkage caused by a high-temperature heat treatment of 150°C or more. The photosensitive resin composition contains the compound of component (B). Therefore, when the photosensitive resin composition is irradiated with active energy rays (e.g., ultraviolet rays), the reaction is difficult to proceed at an irradiation dose below a certain level. At an irradiation dose exceeding the certain level, the reaction proceeds rapidly, the photosensitive resin composition is fully cured, and a cured product can be obtained in which film reduction after development is suppressed.

[0057] The contrast curve involved in the photosensitive resin composition can be obtained by plotting a graph of the film thickness ratio relative to the irradiation dose of the active energy line. The film thickness ratio refers to the ratio of the film thickness of the cured product after development to the film thickness when the photosensitive resin composition is applied. Since the photosensitive resin composition includes components (A), (B) and (C), in the photosensitive resin composition, when the irradiation dose is below a certain amount, the reaction of the photosensitive resin composition is difficult to proceed, and when the irradiation dose exceeds a certain amount, the reaction proceeds rapidly. Therefore, the photosensitive resin composition presents a contrast curve close to the following ideal contrast curve. That is, in the contrast curve of the photosensitive resin composition, the film thickness ratio rises sharply, and then the film thickness ratio tends to be constant even if the irradiation dose increases. By including components (A), (B) and (C), the photosensitive resin composition presents a contrast curve close to the ideal contrast curve. Therefore, by using the photosensitive resin composition, a fine and precise pattern with an L / S of less than 2μm / 2μm can be formed by photolithography.

[0058] Component (A) modified polyphenylene ether

[0059] The photosensitive resin composition contains (A) a modified polyphenylene ether (PPE) resin having the characteristics represented by the following formula (1) (the PPE resin may also be referred to as component (A) or component (A) PPE resin):

[0060] [Chemistry 5]

[0061]

[0062] Where R 1 ~R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group,

[0063] X represents a q-valent unsubstituted or substituted aromatic hydrocarbon group,

[0064] Y represents an unsubstituted or substituted phenol repeating unit represented by the following formula (2):

[0065] [Chemistry 6]

[0066]

[0067] Where R 4 ~R 7 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkenylcarbonyl group,

[0068] m represents an integer from 1 to 100,

[0069] n represents an integer from 1 to 6,

[0070] q represents an integer from 1 to 4.

[0071] Generally, an x-valent (x represents an integer greater than or equal to 1) hydrocarbon group refers to an x-valent group formed by removing x hydrogen atoms from a hydrocarbon carbon atom. Therefore, the aforementioned q-valent unsubstituted or substituted aromatic hydrocarbon group refers to a 1- to 4-valent group formed by removing 1 to 4 hydrogen atoms from an aromatic hydrocarbon carbon atom, wherein the aromatic hydrocarbon may be substituted or unsubstituted.

[0072] The term "alkyl" refers to a monovalent saturated hydrocarbon group. In this embodiment, the alkyl group is preferably C1-C 10 The alkyl group is more preferably a C1-C6 alkyl group, further preferably a C1-C4 alkyl group, and particularly preferably a C1-C2 alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.

[0073] The term "alkenyl" refers to a monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. In this embodiment, the alkenyl group is preferably C2-C 10 Alkenyl, more preferably C2-C6 alkenyl, further preferably C2-C4 alkenyl. Examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl and 1-hexenyl. The group -CR in the above formula (1) is 1 =CR 2R 3 Also alkenyl.

[0074] The term "alkynyl" refers to a monovalent unsaturated hydrocarbon group having at least one carbon-carbon triple bond. 10 The alkynyl group is more preferably a C2-C6 alkynyl group, and further preferably a C2-C4 alkynyl group. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, isobutynyl, pentynyl, and hexynyl.

[0075] The term "alkenylcarbonyl group" refers to a carbonyl group substituted with the above-mentioned alkenyl group, and examples thereof include acryloyl group and methacryloyl group.

[0076] In component (A), -(Y) m - The portion shown corresponds to the main chain of the PPE resin. Preferably, R 4 and R 6 represents a hydrogen atom, and R 5 and R 7 Represents a methyl group. -(Y) m One end of the moiety shown in - is bonded to the aromatic hydrocarbon group X via an oxygen atom. The other end is bonded to the alkenyl group -CR via n methylene groups. 1 =CR 2 R 3 Combined with substituted phenyl. Alkenyl-CR 1 =CR 2 R 3 The methylene group may be located at any of the ortho, meta, and para positions. In one aspect, n in formula (1) is an integer from 1 to 4. In one aspect, n in formula (1) is 1 or 2. In one aspect, n in formula (1) is 1. In another aspect, R in formula (1) 1 ~R 3 They are all hydrogen atoms.

[0077] Furthermore, the number m of the repeating units Y in formula (1) is preferably 1-80, more preferably 1-30, and even more preferably 1-5.

[0078] In the component (A), the aromatic hydrocarbon group X of the formula (1) is connected to q -(Y) via each oxygen atom. m - is combined with the moiety shown in FIG. Preferably, q is 2 or 3. More preferably, q is 2. In addition, X preferably has a structure shown in the following formula:

[0079] [Chemistry 7]

[0080]

[0081] Where R 11~R 18 Each independently represents a hydrogen atom or a C1-C6 alkyl group. More preferably, X has a structure represented by the following formula:

[0082] [Chemistry 8]

[0083]

[0084] From the perspectives of fluidity during molding of the photosensitive resin composition, dielectric properties and heat resistance of the cured product obtained by curing the photosensitive resin composition, and compatibility of other components contained in the photosensitive resin composition, the number average molecular weight of component (A) is preferably 500 or more and 5000 or less. When the number average molecular weight of component (A) is too low, there is a situation where the toughness of the cured product obtained by curing the photosensitive resin composition is reduced. On the other hand, when the number average molecular weight of component (A) is too high, there is a situation where the compatibility of component (A) with respect to other components (for example, any added solvent) is reduced. For example, there is a situation where it becomes difficult to add a solvent to the photosensitive resin composition to make its viscosity suitable for spin coating, etc. The number average molecular weight of component (A) is more preferably 750 or more and 3000 or less, and further preferably 1000 or more and 2500 or less. The number average molecular weight of component (A) can be measured by, for example, gel permeation chromatography.

[0085] The content of component (A) in the photosensitive resin composition is preferably 30.0% to 98.0% by mass, more preferably 35.0% to 97.0% by mass, further preferably 40.0% to 96.0% by mass, and particularly preferably 45.0% to 95.0% by mass, relative to 100% by mass of the photosensitive resin composition. When the content of component (A) is 30.0% to 98.0% by mass relative to 100% by mass of the photosensitive resin composition, a cured product having a low dielectric constant and a low dielectric loss tangent can be obtained, that is, a cured product having excellent electrical properties suitable for use in a high-frequency range.

[0086] As component (A), a commercial product can be used. As a commercial product of component (A), for example, OPE2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) can be used. Component (A) can be prepared by a known method. For example, component (A) can be prepared by the following method. In this method, a compound having X-(OH) q (wherein X and q have the same meanings as above) and suitable q-valent phenols (such as 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol) having a structure represented by the following formula:

[0087] [Chemistry 9]

[0088]

[0089] Where R 4 ~R 7 Each has the same meaning as above. The method comprises oxidative copolymerization of these phenols by a known method to prepare a polyphenylene ether resin having a terminal hydroxyl group. The method also comprises modifying the obtained resin by reacting with an appropriate modifier (e.g., chloromethylstyrene).

[0090] Component (B) silsesquioxane compound

[0091] The photosensitive resin composition contains (B) a compound represented by the following formula (3):

[0092] [Chemistry 10]

[0093]

[0094] The compound represented by formula (3) has a specific cage-shaped silsesquioxane structure and contains eight (meth)acryloylalkyl groups, specifically acryloyloxypropyl groups. The compound represented by formula (3) as component (B) is sometimes also referred to as the component (B) silsesquioxane compound. The molecular weight of the component (B) silsesquioxane compound is preferably 2000 or less, and more preferably 1000 to 2000.

[0095] In the photosensitive resin composition, the mass ratio (A / A+B) of component (A) relative to the total amount of component (A) and component (B) is preferably 0.10 to 0.99, more preferably 0.20 to 0.98, further preferably 0.30 to 0.97, further preferably 0.40 to 0.96, and particularly preferably 0.50 to 0.96. In the photosensitive resin composition, when the mass ratio (A / A+B) of component (A) relative to the total amount of component (A) and component (B) is in the range of 0.10 to 0.99, a cured product in which film reduction after development is suppressed can be obtained by irradiating the photosensitive resin composition with active energy rays (e.g., ultraviolet rays). In addition, by using the photosensitive resin composition, a fine and precise pattern with an L / S of 2 μm / 2 μm or less can be formed by photolithography.

[0096] When the photosensitive resin composition contains the bifunctional acrylic resin (component (D)) described below, the mass ratio of component (A) (A / A+B+D) relative to the total amount of components (A), (B), and (D) is preferably 0.10 to 0.99, more preferably 0.20 to 0.98, even more preferably 0.30 to 0.97, even more preferably 0.40 to 0.96, and particularly preferably 0.50 to 0.96. When the mass ratio of component (A) relative to the total amount of components (A), (B), and (D) is within the above range, the film-forming properties of the photosensitive resin composition are improved. Therefore, a cured product can be obtained in which film reduction after development is suppressed by irradiation with active energy rays.

[0097] The content of component (B) in the photosensitive resin composition is preferably 1.0% to 60.0% by mass, more preferably 2.0% to 58.0% by mass, further preferably 3.0% to 55.0% by mass, and particularly preferably 4.0% to 50.0% by mass, relative to 100% by mass of the photosensitive resin composition. When the content of component (B) in 100% by mass of the photosensitive resin composition is 1.0% to 60.0% by mass, a cured product in which film reduction after development is suppressed can be obtained by irradiating the photosensitive resin composition with active energy rays (e.g., ultraviolet rays) without requiring high-temperature heat treatment at, for example, 150°C or higher. In addition, by using the photosensitive resin composition, a fine and precise pattern with an L / S of 2 μm / 2 μm or less can be formed by photolithography.

[0098] As component (B), a commercially available product can be used. Examples of commercially available products of component (B) include the POSS (Polyhedral Oligomeric silsesquioxane) series manufactured by Hybrid. Specifically, Acrylo POSS Cage Mixture MA0736 (manufactured by Hybrid Plastics Inc.) can be used.

[0099] Component (C) photopolymerization initiator

[0100] The photosensitive resin composition contains (C) a photopolymerization initiator. Component (C) may be a compound that generates free radicals that react component (A), component (B), and, if necessary, component (D) by irradiation with active energy rays. Here, active energy rays include all broadly defined light, such as radiation such as α-rays and β-rays, electromagnetic waves such as γ-rays and X-rays, electron beams (EB), and visible light of about 100 nm to 400 nm, preferably ultraviolet rays. As component (C), one photopolymerization initiator may be used, or two or more photopolymerization initiators may be used in combination.

[0101] As component (C), in order to promote the reaction of component (A), component (B), and, if necessary, component (D) by irradiation with active energy rays, it is preferred to use at least one selected from the group consisting of oxime ester polymerization initiators, acylphosphine oxide polymerization initiators, and alkylphenone polymerization initiators.

[0102] Examples of oxime ester polymerization initiators include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-, 1-(O-acetyl oxime), 1,2-octanedione, and 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyl oxime).

[0103] Examples of the acylphosphine oxide-based polymerization initiator include bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

[0104] Examples of the alkylphenone-based polymerization initiator include 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone.

[0105] The content of component (C) in the photosensitive resin composition is preferably 1.0% to 20.0% by mass, more preferably 3.0% to 18.0% by mass, and even more preferably 5.0% to 15.0% by mass, relative to 100% by mass of the photosensitive resin composition. When the content of component (C) in 100% by mass of the photosensitive resin composition is 1.0% to 20.0% by mass, a cured product can be obtained by irradiating the photosensitive resin composition with active energy rays (e.g., ultraviolet rays) without requiring high-temperature heat treatment at, for example, 150°C or higher.

[0106] As component (C), commercially available products can be used. Examples of commercially available products of component (C) include Irgacure OXE-01 (manufactured by BASF), Irgacure OXE-02 (manufactured by BASF), Omnirad 819 (formerly Irgacure 819) (manufactured by IGM Resins BV), and Omnirad 369 (formerly Irgacure 369) (manufactured by IGM Resins BV).

[0107] Component (D) bifunctional acrylic resin

[0108] The photosensitive resin composition preferably further contains (D) a bifunctional acrylic resin represented by the following formula (4) (the bifunctional acrylic resin may also be described as component (D) or component (D) bifunctional acrylic resin):

[0109] [Chemistry 11]

[0110]

[0111] In the formula, each R a independently represents a hydrogen atom or a methyl group,

[0112] Each R b independently represent a divalent hydrocarbon group,

[0113] x and y each independently represent an integer of 1 to 5.

[0114] R in formula (4) b Each independently is preferably methylene or p-phenylene. b can be methylene, and R a It can also be methyl. b can be phenylene, and R a A hydrogen atom may also be used.

[0115] When the photosensitive resin composition contains a bifunctional acrylic resin as component (D), when the photosensitive resin composition is irradiated with active energy rays (such as ultraviolet rays), the reaction is difficult to proceed at an irradiation dose below a certain amount. When the irradiation dose exceeds a certain amount, the reaction proceeds rapidly, and component (D) and component (B) react fully with component (A) together, so that a cured product with further suppressed film reduction after development can be obtained. Component (D) is bifunctional, that is, it has two acryloyl groups. Therefore, for example, even if component (A) is a low molecular weight, after component (A) and component (B) react rapidly, component (A) that has not yet reacted will react with component (D). Therefore, the formability of the pattern formed by photolithography is good, and a cured product with further suppressed film reduction after development can be obtained. When the photosensitive resin composition contains component (D), a low molecular weight component (A) can be used. Therefore, the film-forming property of the photosensitive resin composition can be improved. Therefore, a film of the photosensitive resin composition can be formed by a relatively simple method such as spin coating. In a monofunctional acrylic resin having one acryloyl group per molecule, after the reaction between component (A) and component (B), there is a case where the reaction between component (A) and the monofunctional acrylic resin does not proceed due to unreacted components (A), resulting in a decrease in the film after development. Even in a polyfunctional acrylic resin having three or more acryloyl groups per molecule, the number of functional groups is too large, and after the reaction between component (A) and component (B), there is a case where the reaction between component (A) and the polyfunctional acrylic resin having three or more acryloyl groups per molecule does not proceed due to unreacted components (A), resulting in a decrease in the film after development.

[0116] Examples of component (D) include ethoxylated bisphenol A diacrylate (bisphenol A diacrylate bonded to (poly)ethylene glycol), propoxylated bisphenol A diacrylate (bisphenol A diacrylate bonded to (poly)propylene glycol), ethoxylated neopentyl glycol diacrylate (neopentyl glycol diacrylate bonded to (poly)ethylene glycol), and propoxylated neopentyl glycol diacrylate (neopentyl glycol diacrylate bonded to (poly)propylene glycol). As these bifunctional acrylic resins (component (D),) one type of resin may be used, or two or more types of resins may be used in combination.

[0117] In the photosensitive resin composition, the mass ratio (D / B+D) of component (D) relative to the total amount of component (B) and component (D) is preferably 0.01 to 0.99, more preferably 0.02 to 0.80, further preferably 0.03 to 0.70, and even more preferably 0.04 to 0.60. When the photosensitive resin composition contains component (D), when the mass ratio (D / B+D) of component (D) relative to the total amount of component (B) and component (D) is in the range of 0.01 to 0.99, the film-forming properties of the photosensitive resin composition are good. Therefore, by irradiating the photosensitive resin composition with active energy rays (e.g., ultraviolet rays), a cured product can be obtained in which film reduction after development is further suppressed.

[0118] The content of component (D) in the photosensitive resin composition is preferably 59.0% by mass or less, more preferably 1.0% to 57.0% by mass, further preferably 3.0% to 55.0% by mass, and even more preferably 5.0% to 50.0% by mass relative to 100% by mass of the photosensitive resin composition. When the photosensitive resin composition contains component (D), when the content of component (D) in 100% by mass of the photosensitive resin composition is 59.0% by mass, the film-forming property of the photosensitive resin composition is good. Therefore, by irradiating the photosensitive resin composition with active energy rays (such as ultraviolet rays), a cured product in which the film reduction after development is further suppressed can be obtained.

[0119] As component (D), commercially available products can be used. As commercially available products of component (D), for example, ethoxylated (4) bisphenol A diacrylate SR601 (manufactured by Sartomer Chemical Co.) and propoxylated (2) neopentyl glycol diacrylate SR9003B (manufactured by Sartomer Chemical Co.) can be used. Component (D) can be prepared by a known method. For example, it can be prepared by including a (CH3)2(CR b OH)2(where R b Component (D) can be prepared by reacting an appropriate diol compound having a structure represented by (a) (having the same meaning as above) with acrylic acid or a derivative thereof.

[0120] Component (E): crystalline or amorphous thermoplastic resin

[0121] The photosensitive resin composition may further include a crystalline or amorphous thermoplastic resin as component (E), but the thermoplastic resin does not include a bifunctional acrylic resin. This thermoplastic resin is sometimes also referred to as component (E) or component (E) thermoplastic resin. By including the thermoplastic resin as component (E) in the photosensitive resin composition, for example, the temperature characteristics of the photosensitive resin can be improved, and the moldability of the photosensitive resin composition can also be improved.

[0122] Examples of the crystalline thermoplastic resin as component (E) include at least one selected from the group consisting of liquid crystal polymers, polyethylene, polypropylene, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyetherketone, and polytetrafluoroethylene. Examples of the amorphous thermoplastic resin as component (E) include at least one selected from the group consisting of polyvinyl chloride, polystyrene, polymethyl methacrylate, acrylonitrile-butadiene-styrene, polycarbonate, polyethersulfone, polyetherimide, and polyamideimide. As the thermoplastic resin as component (E), one resin may be used, or two or more resins may be used in combination.

[0123] The content of component (E) in the photosensitive resin composition is preferably 40.0% by mass or less, preferably 1.0% to 35.0% by mass, more preferably 2.0% to 30.0% by mass, further preferably 3.0% to 25.0% by mass, and even more preferably 5.0% to 20.0% by mass, relative to 100% by mass of the photosensitive resin composition. When the content of component (E) in 100% by mass of the photosensitive resin composition is 40.0% by mass or less, a cured product with suppressed film reduction after development can be obtained by irradiating the photosensitive resin composition with active energy rays (e.g., ultraviolet rays). Furthermore, other properties of the photosensitive resin composition, such as temperature characteristics and formability, can be improved.

[0124] Component (F) coupling agent

[0125] The photosensitive resin composition may contain a coupling agent. A coupling agent is a compound having two or more different functional groups in one molecule. One of the functional groups is a functional group that chemically bonds with an inorganic material, and the other is a functional group that chemically bonds with an organic material. The inclusion of a coupling agent in the photosensitive resin composition can improve the adhesion between the photosensitive resin composition and other materials. In this specification, a coupling agent is sometimes referred to as component (F) or component (F) coupling agent.

[0126] Examples of the coupling agent as component (F) include at least one selected from the group consisting of silane coupling agents, aluminum coupling agents, and titanium coupling agents. As component (F), one coupling agent may be used alone, or two or more coupling agents may be used in combination.

[0127] Component (F) is preferably a silane coupling agent. Examples of functional groups possessed by the silane coupling agent include alkoxy, vinyl, epoxy, styryl, methacrylate, acrylate, amino, isocyanurate, urea, mercapto, thioether, and isocyanate groups.

[0128] The content of component (F) in the photosensitive resin composition is preferably 30.0% by mass or less, more preferably 0.10% to 30.0% by mass, further preferably 0.20% to 20.0% by mass, further preferably 0.50% to 10.0% by mass, and particularly preferably 0.80% to 3.0% by mass, relative to 100% by mass of the photosensitive resin composition. When the photosensitive resin composition contains component (F), when the content of component (F) in 100% by mass of the photosensitive resin composition is 30.0% by mass or less, the adhesion between the photosensitive resin composition and other materials becomes good. For example, substrates and the like can be cited as other materials.

[0129] As component (F), commercially available products can be used. Examples of commercially available products of component (F) include 3-methacryloxypropyltrimethoxysilane KBM 503, vinyltrimethoxysilane KBM 1003 (manufactured by Shin-Etsu Silicone Co., Ltd.), and Coatsil MP200 Silane (manufactured by Momentive Advanced Materials Japan Co., Ltd.).

[0130] In order to impart flexibility, a film-forming agent can be added to the photosensitive resin composition. For example, when a photosensitive resin composition is used to form an insulating layer of a wiring structure, when flexibility is imparted to the photosensitive resin composition by adding a film-forming agent, a film is easily formed, and a thin film can be easily formed. As examples of film-forming agents, at least one selected from the group consisting of phenoxy resins and acrylic resins (but excluding the bifunctional acrylic resins shown in formula (4)) can be cited. As phenoxy resins, polyhydroxy polyethers can be cited. The polyhydroxy polyethers are synthesized by direct reaction of a dihydric phenol compound with epichlorohydrin, or by addition polymerization of a dihydric phenol compound with diglycidyl ether. Acrylic resins (but excluding the bifunctional acrylic resins shown in formula (4)) refer to homopolymers or copolymers of acrylic acid and / or methacrylic acid or their derivatives (such as esters and amides). Commercially available products can also be used as film-forming agents. Examples of commercially available film-forming agents include bisphenol A phenoxy resin 4250 (manufactured by Mitsubishi Chemical Corporation), bisphenol A phenoxy resin Fx316 (manufactured by Nippon Steel Chemicals Co., Ltd.), bisphenol A phenoxy resin YP50 (manufactured by Nippon Steel Chemicals Co., Ltd.), and polymethyl methacrylate-butylacrylamide-triblock copolymer Nanostrength (registered trademark) M52N (manufactured by ARKEMA).

[0131] The photosensitive resin composition may further contain at least one additive selected from the group consisting of an ion trapping agent, a leveling agent, an antioxidant, and a thixotropic agent, as needed. Furthermore, the photosensitive resin composition may also contain a viscosity modifier, a flame retardant, a solvent, and the like.

[0132] Method for producing photosensitive resin composition

[0133] The photosensitive resin composition can be manufactured by mixing component (A), component (B) and component (C). As needed, the photosensitive resin composition can be manufactured by mixing at least one component selected from the group consisting of component (D), component (E) and component (F) with component (A), component (B) and component (C). The method for manufacturing the photosensitive resin composition is not particularly limited. The photosensitive resin composition can be manufactured by mixing the raw materials of each component with a mixer such as a crusher, a pot mill, a three-roll mill, a hybrid mixer, a rotary mixer or a double-shaft mixer. These components can be mixed simultaneously, or a part can be mixed first and then the remaining part can be mixed. In addition, the photosensitive resin composition can also be manufactured by appropriately combining the above-mentioned devices.

[0134] Cured material

[0135] By irradiating the photosensitive resin composition with active energy rays, a cured product can be obtained. A uniform thin film of the photosensitive resin composition can be formed by a relatively simple film-forming method such as spin coating. On the thin film formed using the photosensitive resin composition, patterning is performed using photolithography to form a fine and precise pattern. The photosensitive resin composition can be fully cured by irradiation with active energy rays. There is no need to treat the patterned film with high temperature (for example, above 150°C). Therefore, deformation of the wiring pattern caused by shrinkage during high-temperature treatment can be suppressed.

[0136] In the cured product obtained by curing the photosensitive resin composition, it is preferred that the relative dielectric constant (ε) is, for example, less than 3.0, and the dielectric loss tangent (tan δ) is, for example, less than 0.01. Since the electrical properties of the cured product with low dielectric constant and low dielectric loss tangent are good when used in a high frequency range, it can be used for electronic components or semiconductor devices used in a high frequency range. In addition, when the photosensitive resin composition is irradiated by active energy lines (such as ultraviolet rays), the reaction is difficult to proceed at an irradiation dose below a certain quantitative amount. When the irradiation dose exceeds a certain quantitative amount, the reaction proceeds rapidly, and the photosensitive resin composition is fully cured, and the film after development can be obtained to reduce the suppressed cured product. Therefore, the photosensitive resin composition can be suitable for use as a material (for example, a material for an insulating layer) for forming a rewiring layer. The photosensitive resin composition can be suitable for use as a material for forming a wiring structure containing a rewiring layer.

[0137] The photosensitive resin composition can also be used as an interlayer adhesive film between multilayer wirings in a wiring structure. In addition, the photosensitive resin composition can be used for bonding and sealing components constituting semiconductor devices, camera modules, or image sensor modules.

[0138] The embodiment of the present disclosure can provide a photosensitive resin composition, a cured product thereof, a wiring structure containing a cured product thereof, an electronic component containing a cured product thereof, a semiconductor device containing a cured product thereof, and a camera module containing a cured product thereof. As an electronic component, for example, an electronic component comprising a wiring structure for an electronic device (such as a mobile phone, a smart phone, a notebook computer, a tablet terminal, etc.) can be cited. As a semiconductor device, a memory device such as D-RAM (Dynamic Random Access Memory, dynamic random access memory), a processor device such as a CPU (Central Processing Unit, central processing unit) GPU (Graphics Processing Unit, graphics processing unit), a light-emitting element such as LED (Light Emitting Diode, light-emitting diode), and a driver IC used in LCD (Liquid Crystal Display, liquid crystal display), etc. can be cited.

[0139] Method for producing cured product

[0140] An example of a method for producing a cured product using a photosensitive resin composition will be described. The method for producing a cured product may include a step of applying the photosensitive resin composition to an object, a preheating step (soft baking), an irradiation step with active energy rays, and a development step. The object to be coated with the photosensitive resin composition may not be surface treated prior to application. The method for producing a cured product may include a surface treatment step for the object.

[0141] Surface treatment process of objects

[0142] Examples of the object include semiconductor wafers. The semiconductor wafer may be subjected to a surface activation treatment. Examples of the surface activation treatment include plasma activation treatment. By surface treating the object, the bonding strength between the photosensitive resin composition and the object can be increased.

[0143] Coating process

[0144] The photosensitive resin composition is preferably applied to an object that has been surface-treated. Apparatus for applying the photosensitive resin composition include screen printers, dispensers, and spin coaters (e.g., Headway Spinner (manufactured by Headway Research, Inc.) and WS-650-8B (manufactured by Laurell)). During the coating process, the photosensitive resin composition is preferably applied to form a uniform thin film on the surface of the object.

[0145] Preheating treatment (soft baking)

[0146] The photosensitive resin composition applied to the object may be preheated (soft-baked) before irradiation with active energy rays. The preheating temperature may be 80°C or higher and less than 150°C, or 100°C to 140°C. The preheating may be performed using a hot plate or a convection oven (hot air circulation dryer). The heat treatment time is 1 to 10 minutes, preferably 5 to 10 minutes.

[0147] Irradiation process

[0148] After the above-mentioned preheating treatment is performed as needed, the photosensitive resin composition coated on the object is preferably irradiated with active energy rays to obtain a cured product. A patterned cured product can be formed by photolithography using a photomask. Examples of active energy rays include ultraviolet rays of 10 nm to 380 nm and visible light of 380 nm to 760 nm. The wavelength of the active energy ray that cures the photosensitive resin composition is preferably 10 nm to 600 nm, more preferably 100 nm to 500 nm, further preferably 250 nm to 450 nm, and particularly preferably 300 nm to 400 nm. The atmospheric temperature during irradiation with active energy rays can be 0°C to 100°C, 10°C to 50°C, or 15°C to 35°C. The time for irradiating the active energy ray varies depending on the volume of the irradiated object, etc., and is generally 5 seconds to 60 minutes.

[0149] Development process

[0150] After the active energy ray irradiation, the photomask is preferably removed and the uncured photosensitive resin composition is washed with a developer or a solvent to obtain a cured product with a pattern formed thereon. A solvent can be used as a developer. Examples of solvents that can be used as a developer include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like. Examples of alcohol solvents include C1-C4 alcohol, 4-methyl-2-pentanol, and n-hexanol. 18 Monoalcohol solvents; and C2~C 18Polyol solvents. Examples of ether solvents include dialkyl ether solvents such as diethyl ether and dipropyl ether; cyclic ether solvents such as tetrahydrofuran; and aromatic ether solvents such as diphenyl ether. Examples of ketone solvents include chain ketone solvents such as acetone, butanone, and methyl isobutyl ketone; and cyclic ketone solvents such as cyclopentanone and cyclohexanone. Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; and chain amide solvents such as N-methylformamide and N,N-dimethylformamide. Examples of ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate; polyol partial ether acetate solvents such as diethylene glycol mono-n-butyl ether acetate and propylene glycol monomethyl ether acetate; and lactone solvents such as γ-butyrolactone. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-hexane; and aromatic hydrocarbon solvents such as benzene and toluene. As solvents that can be used as developer solutions, ketone solvents or ester solvents are preferably used. As a solvent that can be used as a developer, cyclopentanone, cyclohexanone or propylene glycol monomethyl ether acetate is preferable. After washing with a solvent, a washing (rinsing) treatment can be further performed using deionized water or the like.

[0151] Embodiments of the present disclosure can provide a photosensitive resin composition, a cured product thereof, a wiring structure containing the cured product thereof, an electronic component containing the cured product thereof, a semiconductor device containing the cured product thereof, and a camera module containing the cured product thereof.

[0152] Example

[0153] The following examples further illustrate the embodiments of the present disclosure. The technology of the present disclosure is not limited to these examples. In the following examples and comparative examples, the numbers representing the proportions of the components contained in the photosensitive resin composition are all expressed in parts by mass.

[0154] Ingredient (A): Modified polyphenylene ether (PPE) resin

[0155] A-1: OPE 2st 1200 (represented by formula (1), a modified polyphenylene ether resin having vinyl groups at both ends (reaction product of 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol and 2,6-dimethylphenol condensate and chloromethylstyrene, number average molecular weight 1160)) (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0156] Component (B): Silsesquioxane compound

[0157] B-1: Acrylo POSS Cage Mixture MA0736 (represented by formula (3), comprising a compound having a cage-shaped silsesquioxane structure and having 8 acryloxypropyl groups) (manufactured by Hybrid Plastic Inc.)

[0158] Component (C): Photopolymerization initiator

[0159] C-1: Irgacure OXE-02 (oxime ester photopolymerization initiator, manufactured by BASF)

[0160] C-2: Omnirad 819 (formerly Irgacure 819) (acylphosphine oxide-based photopolymerization initiator, manufactured by IGM Resins BV)

[0161] C-3: Omnirad 369 (formerly Irgacure 369) (alkylphenone-based photopolymerization initiator, manufactured by IGM Resins B.V.)

[0162] Component (D): Bifunctional acrylic resin

[0163] D-1: SR9003B (propoxylated (2) neopentyl glycol diacrylate, manufactured by Sartomer Chemical Co.)

[0164] D-2: SR601 (ethoxylated (4) bisphenol A diacrylate, manufactured by Sartomer Chemical Co.)

[0165] Examples 1 to 12, Comparative Examples 1 to 4

[0166] Component (A), component (B), component (C), and, if necessary, component (D) were mixed in the ratios shown in Tables 1 to 3 using a rotation / revolution mixer (ARE-310, Shinki Co., Ltd.) to produce the photosensitive resin compositions of Examples and Comparative Examples.

[0167] Production of cured products: coating process and preheating process

[0168] Using each of the photosensitive resin compositions of Examples and Comparative Examples, a cured product constituting a wiring pattern was produced by photolithography.

[0169] First, a silicon wafer having a diameter of 150 mm was prepared as an object.

[0170] Each of the photosensitive resin compositions of Examples and Comparative Examples was spin-coated onto a silicon wafer using a spin coater (WS-650-8B, manufactured by Laurell). During spin coating, the spin coater was operated at 500 rpm for 12 seconds and then at 1500 rpm for 20 seconds. Thus, a thin film of the photosensitive resin composition was formed on the surface of the silicon wafer.

[0171] Next, the silicon wafer with the photosensitive resin composition thin film was preheated (soft-baked) at 120°C for 5 minutes in an air atmosphere to dry the photosensitive resin composition. This yielded a sample of a photosensitive resin composition thin film with a film thickness of 13 μm. The film thickness of the photosensitive resin composition thin film was measured using a stylus profilometer (DektakXT, manufactured by BRUKER).

[0172] The sample was used to perform the subsequent photolithography test, and a cured product was obtained by photolithography.

[0173] Production of cured products: irradiation process

[0174] Photolithography test

[0175] A mask (1951 USAF resolution test chart, 1.5 mm thick, manufactured by Advance Reproductions) was placed on the surface of a film composed of the sample's photosensitive resin composition. While the mask was in close contact with the film's surface, the sample was irradiated with ultraviolet light under the following conditions. The mask was provided with numerous rectangular areas (450 μm x 450 μm). Two wiring patterns were formed in each of these areas, each with three straight lines arranged in parallel. The two wiring patterns, each with three straight lines arranged in parallel, were arranged in directions perpendicular to each other. Each wiring pattern in these areas consisted of three straight lines with an L / S ratio of 2 μm / 2 μm.

[0176] UV irradiation conditions

[0177] Ultraviolet irradiation device: Bluewave (registered trademark) QX4 (manufactured by DYMAX)

[0178] (As a light source, LED Heads Redicure (registered trademark) (manufactured by DYMAX) were installed.)

[0179] Active energy rays: Ultraviolet rays: wavelength 365nm

[0180] Radiation dose: 135mJ / cm 2

[0181] Irradiation time: 10 seconds

[0182] Distance between mask and light source: 45μm

[0183] Production of cured products: Development process

[0184] After the ultraviolet irradiation is completed, the mask is removed from the sample. The following development treatment is performed: propylene glycol monomethyl ether acetate (2PGMEA) is used as a developer to wash away the uncured photosensitive resin composition on the sample. In the development treatment, two development treatments are performed: one 50-second development treatment and two 50-second development treatments. In the one 50-second development treatment, the sample is immersed in a developer in an amount that can immerse the entire sample for 50 seconds. In the two 50-second development treatments, the sample is immersed in the developer for 50 seconds, then the sample is taken out of the developer, and after natural drying in an atmospheric atmosphere, the sample is immersed in the developer again for 50 seconds. After the development treatment, the sample is taken out of the developer and naturally dried in an atmospheric atmosphere. Thus, a cured product having a wiring pattern structure is obtained.

[0185] Evaluation Method

[0186] The films and cured products obtained by the above-mentioned method for producing a cured product were evaluated as follows. The evaluation results are shown in the table.

[0187] Film-forming property (appropriate film formation)

[0188] The film thickness of the thin film formed by spin-coating each photosensitive resin composition of Examples and Comparative Examples on a silicon wafer was visually confirmed. Then, the film-forming properties of each photosensitive resin composition of Examples and Comparative Examples were evaluated as follows.

[0189] Good: A uniform thin film is formed on the entire surface of the silicon wafer.

[0190] Poor: There is a portion where the thin film is not formed on a part of the silicon wafer surface.

[0191] Patternability

[0192] The cured product after the photolithography test was observed and photographed using a scanning electron microscope (SEM), and patterning properties were confirmed from the SEM photographs obtained by the photographing. Figure 1 This is an enlarged view showing an example of a three-line pattern with an L / S ratio of 2 μm / 2 μm. The patterning properties of the cured products described in Examples and Comparative Examples were evaluated as follows.

[0193] Good: In the SEM photograph, it was confirmed that a three-line pattern with L / S of 2 μm / 2 μm was formed.

[0194] Good: In the SEM photograph, it was confirmed that the three-line pattern included a pattern where L / S was not 2 μm / 2 μm, but a three-line pattern was formed.

[0195] Poor: In the SEM photograph, it was confirmed that a three-line pattern was not formed, but a pattern with a shape resembling an extruded deformation was formed.

[0196] Contrast curve

[0197] In the photolithography test, the photosensitive resin compositions of Examples and Comparative Examples were used, and the UV irradiation dose (mJ / cm 2 ), a cured product was obtained. The film thickness ratio under each irradiation dose was measured, that is, the ratio of the film thickness of the cured product after ultraviolet irradiation to the film thickness of the thin film of the photosensitive resin composition before ultraviolet irradiation. A graph was drawn to show the relationship between the irradiation dose and the film thickness ratio. As mentioned above, the film thickness of the thin film of the photosensitive resin composition before ultraviolet irradiation is 13 μm. The film thickness of the cured product after ultraviolet irradiation was measured as follows. That is, one cross section of the 3-line pattern formed in the sample was observed and photographed using an SEM. The thickness from the surface of the silicon wafer to the top of the pattern was derived from the cross-sectional SEM photograph obtained by the photographing, and the thickness was measured as the film thickness of the cured product. In an ideal comparison curve, the photosensitive resin composition does not react at an irradiation dose below a certain amount, and the reaction proceeds rapidly when the irradiation dose exceeds a certain amount, and the film thickness ratio rises rapidly relative to the irradiation dose. In addition, in the ideal comparison curve, even if the irradiation dose is further increased, the film thickness ratio is constant, and it can be confirmed that the reaction has reached saturation. The comparison curve showing the relationship between the irradiation dose and the film thickness ratio when the photosensitive resin compositions of the embodiments and comparative examples are cured was evaluated as follows.

[0198] Excellent: In the comparison curve showing the relationship between irradiation dose and film thickness ratio, the irradiation dose is 30mJ / cm 2 When the film thickness ratio is close to 0, the irradiation dose exceeds 30mJ / cm 2 and increased to 50 mJ / cm 2 Up to 100mJ / cm 2 When the film thickness ratio increases by more than 40%.

[0199] Good: In the comparison curve showing the relationship between irradiation dose and film thickness ratio, the irradiation dose is 30mJ / cm 2 When the film thickness ratio is 1% to 10% and the irradiation dose exceeds 30mJ / cm 2 and increased to 50 mJ / cm 2 Up to 100mJ / cm 2 When the film thickness ratio increases by more than 40%.

[0200] Poor: In the comparison curve showing the relationship between irradiation dose and film thickness ratio, even at a irradiation dose of 30mJ / cm 2 Below, the film thickness ratio exceeds 10%; even if the irradiation dose exceeds 30mJ / cm2 and increased to 50 mJ / cm 2 Up to 100mJ / cm 2 , the increase in film thickness ratio is less than 40%. Relative dielectric constant (ε), dielectric loss tangent (tanδ)

[0201] Assay samples were prepared as follows.

[0202] The photosensitive resin composition was applied onto a support and preheated (soft-baked) at 120° C. for 5 minutes in an air atmosphere to dry the photosensitive resin composition by heating. Thus, a 13 μm-thick photosensitive resin composition film was obtained.

[0203] The relative dielectric constant (ε) and dielectric loss tangent (tan δ) of the sample were measured at a dielectric resonance frequency of 10 GHz using a separated pillar dielectric resonator (SPDR). The relative dielectric constant (ε) is preferably 1.5 to 3.3, more preferably 1.5 to 2.8. The dielectric loss tangent (tan δ) is preferably 0.001 to 0.010.

[0204] [Table 1]

[0205]

[0206] [Table 2]

[0207]

[0208] [Table 3]

[0209]

[0210] As shown in Tables 1 to 3, the photosensitive resin compositions of Examples 1 to 12 have excellent film-forming properties (film formation) and patterning properties. Furthermore, the photosensitive resin compositions of Examples 1 to 12 are fully cured by ultraviolet irradiation, and a cured product in which the film reduction after development is suppressed can be obtained. In addition, the photosensitive resin compositions of Examples 1 to 12 have low relative dielectric constants (ε) and dielectric loss tangents (tanδ), so the electrical properties when used in a high-frequency range are good. In the photosensitive resin compositions of Examples 1 to 12, the comparison curves showing the relationship between the film thickness ratio and the irradiation dose are close to the ideal comparison curves. That is, in these comparison curves, at an irradiation dose below a certain amount, the reaction of the photosensitive resin composition is difficult to proceed. When the irradiation dose exceeds a certain amount, the reaction proceeds rapidly, and the film thickness ratio rises sharply. Thereafter, even if the irradiation dose is further increased, the film thickness ratio tends to be constant. Therefore, according to the photosensitive resin compositions of Examples 1 to 12, a fine and precise pattern with an L / S of 2 μm / 2 μm or less can be formed by photolithography.

[0211] Figure 2 This is a graph showing the comparative curves of each cured product obtained using the photosensitive resin compositions of Example 6, Example 7, and Example 12. This comparative curve shows the relationship between the film thickness ratio and the irradiation dose when a development treatment of 50 seconds is performed once and a development treatment of 50 seconds is performed twice. It can be confirmed that the photosensitive resin composition of the same example shows the same trend of comparative curve even when a development treatment of 50 seconds is performed once and a development treatment of 50 seconds is performed twice. Figure 2 As shown, the photosensitive resin composition of Example 6 exhibits a comparative curve close to the ideal comparative curve. That is, in the comparative curve of Example 6, the reaction of the photosensitive resin composition is difficult to proceed at an irradiation dose below a certain amount. When the irradiation dose exceeds a certain amount, the reaction proceeds, and even if the irradiation dose is further increased, the film thickness ratio tends to be constant. The photosensitive resin composition of Example 7 exhibits a comparative curve even closer to the ideal comparative curve. That is, in the comparative curve of Example 7, the reaction of the photosensitive resin composition is difficult to proceed at an irradiation dose below a certain amount. When the irradiation dose exceeds a certain amount, the reaction proceeds rapidly, the film thickness ratio increases sharply, and even if the irradiation dose is further increased, the film thickness ratio tends to be constant. The photosensitive resin composition of Example 12, because it contains component (D) a bifunctional acrylic resin, exhibits a comparative curve close to the ideal comparative curve when irradiated with ultraviolet light. That is, in the comparative curve of Example 12, after the curing is completed rapidly, the components (A) and (D) that have not yet reacted also react, and the film thickness ratio slowly increases.

[0212] As shown in Tables 1 and 3, the photosensitive resin compositions of Comparative Examples 1 to 4 did not exhibit contrast curves close to the ideal contrast curve. The photosensitive resin composition of Comparative Example 2, lacking component (A) PPE, exhibited poor film-forming and patterning properties. The photosensitive resin compositions of Comparative Examples 3 and 4, while containing component (D) bifunctional acrylic resin, did not contain component (B) silsesquioxane compound. Therefore, even when the irradiation dose exceeded a certain level, the reaction did not proceed rapidly, and a contrast curve close to the ideal contrast curve could not be obtained.

[0213] like Figure 3 As shown, the photosensitive resin composition of Comparative Example 1 does not contain the silsesquioxane compound (B). Therefore, even if the irradiation dose is 30 mJ / cm 2 Even if the irradiation dose exceeds 30mJ / cm 2 and increased to 50 mJ / cm 2 Up to 100mJ / cm 2, the reaction will not proceed as rapidly, and the increase in film thickness ratio will be less than 30%. Therefore, a large amount of irradiation dose must be used before the film thickness ratio reaches a constant. As described above, the photosensitive resin composition of Comparative Example 1 does not show a contrast curve close to the ideal contrast curve.

[0214] Industrial Applicability

[0215] The photosensitive resin composition described in one aspect of the present disclosure does not require high-temperature heat treatment and can be used as an insulating material for wiring. This photosensitive resin composition can be used, for example, as an insulating layer material and interlayer adhesive film for forming a rewiring layer in a wiring structure. Furthermore, the photosensitive resin composition described in one aspect of the present disclosure can be used for bonding and sealing components constituting electronic components, semiconductor devices, camera modules, or image sensor modules.

Claims

1. A photosensitive resin composition comprising the following components (A) to (C): (A) A modified polyphenylene ether resin represented by the following formula (1): [Chemistry 12] Where R 1 ~R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, X represents a q-valent unsubstituted or substituted aromatic hydrocarbon group, Y represents an unsubstituted or substituted phenol repeating unit represented by the following formula (2): [Chemistry 13] Where R 4 ~R 7 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkenylcarbonyl group; m represents an integer from 1 to 100, n represents an integer from 1 to 6, q represents an integer from 1 to 4; (B) a compound represented by the following formula (3): [Chemistry 14] as well as, (C) a photopolymerization initiator; The content of the component (A) is 30.0% by mass to 98.0% by mass, and the content of the component (B) is 1.0% by mass to 60.0% by mass, relative to 100% by mass of the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition further comprises (D) a bifunctional acrylic resin represented by the following formula (4): [Chemistry 15] In the formula, each R a independently represents a hydrogen atom or a methyl group, Each R b independently represent a divalent hydrocarbon group, x and y each independently represent an integer of 1 to 5.

3. The photosensitive resin composition according to claim 1 or 2, wherein The component (C) is at least one selected from the group consisting of acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and alkylphenone-based photopolymerization initiators.

4. The photosensitive resin composition according to claim 1 or 2, wherein The mass ratio of the component (A) relative to the total amount of the component (A) and the component (B) is 0.10 to 0.

99.

5. The photosensitive resin composition according to claim 1 or 2, wherein The content of the component (C) is 1.0% by mass to 20.0% by mass relative to 100% by mass of the photosensitive resin composition.

6. The photosensitive resin composition according to claim 2, wherein The mass ratio of the component (D) to the total amount of the component (B) and the component (D) is 0.01 to 0.

99.

7. The photosensitive resin composition according to claim 1 or 2, wherein The photosensitive resin composition further includes (E) a crystalline or amorphous thermoplastic resin, but the thermoplastic resin does not include a bifunctional acrylic resin.

8. The photosensitive resin composition according to claim 7, wherein The component (E) is at least one selected from the group consisting of liquid crystal polymer, polyethylene, polypropylene, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyetherketone, polytetrafluoroethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, acrylonitrile butadiene styrene, polycarbonate, polyether sulfone, polyetherimide and polyamideimide.

9. The photosensitive resin composition according to claim 1 or 2, wherein The photosensitive resin composition is used to form a wiring structure including a rewiring layer. 10 . A cured product obtained by curing the photosensitive resin composition according to claim 1 .

11. A wiring structure comprising the cured product according to claim 10.

12. An electronic component comprising the cured product according to claim 10.

13. A semiconductor device comprising the cured product according to claim 10.

14. A camera module comprising the cured product according to claim 10.

Images