Airtight structure, method for producing same, and base resin composition for maintaining airtightness

Abstract

The airtight structure of the present disclosure has an airtight portion, a base layer including a cured resin covering an edge portion of the airtight portion, and an ALD layer covering the base layer.

Description

Technical Field

[0001] The present disclosure relates to an airtight structure, a method for producing the same, and an airtight-maintaining base resin composition. Background Art

[0002] In recent years, there has been an increasing trend in the use of microstructures such as MEMS (Micro Electro Mechanical Systems) within hollow structures that maintain airtightness. The hollow structure contains a space that is isolated from the outside world, and the microstructures housed within this space are isolated from the external environment and protected. Furthermore, as specific examples of structures that maintain airtightness, gyroscope sensors, acceleration sensors, SAW (Surface Acoustic Wave) and BAW (Bulk Acoustic Wave) filters, flow path chips, optical waveguide elements, optical elements, and other structures are also known.

[0003] In order to maintain the airtightness in the hollow structure, there is a method of providing an ALD layer using an atomic layer deposition method (ALD) on the outside of the hollow structure (for example, see Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2016-511535 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] The hollow structure can be formed by, for example, metal-bonding the tops of Au or Sn-Cu alloy side wall frames provided on a pair of substrates, or providing resin ribs between the pair of substrates using a permanent resist as the resin material.

[0009] However, when the tops of the metal sidewall frames are metal-bonded to each other, tiny gaps sometimes form in the bonding surface. If these gaps penetrate the inside and outside of the hollow structure, the airtightness within the hollow structure is impaired. In addition, when a hollow structure is formed by forming a resin rib on one side of a pair of substrates and bringing the top of the rib into contact with the other side of the pair of substrates, if the top of the rib is not smooth, a gap penetrating the inside and outside of the hollow structure is generated at the contact portion between the rib and the substrate, thereby also impairing the airtightness within the hollow structure. In addition, sometimes fine cracks form in the resin ribs, which may also damage the airtightness within the hollow structure.

[0010] ALD controls film thickness at the atomic layer level, enabling the formation of flat and dense thin films. Based on the principle of ALD, the film formation rate for even standard aluminum oxide (Al2O3) is approximately 0.11 nm per cycle, or 100 to 300 nm per hour, which is very time-consuming. Therefore, maintaining the airtightness of hollow structures solely through time-consuming ALD thin film formation is unrealistic.

[0011] The present disclosure has been made in view of the above-mentioned conventional situation, and its object is to provide an airtight structure having excellent airtightness and a method for producing the same. In addition, the present disclosure aims to provide an airtight-maintaining base resin composition used in the production of the airtight structure having excellent airtightness.

[0012] Means for solving problems

[0013] Specific means for achieving the above-mentioned objects are as follows.

[0014] <1> An airtight structure includes: an airtight portion; a base layer including a cured resin covering an edge portion of the airtight portion; and an ALD layer covering the base layer.

[0015] <2> according to <1> The airtight structure, wherein the glass transition temperature of the cured resin is 150°C to 400°C.

[0016] <3> according to <1> or <2> The airtight structure, wherein the 5% weight loss temperature of the resin cured product is 250°C to 400°C.

[0017] <4> according to <1> ~ <3> The airtight structure according to any one of the preceding claims, wherein the storage modulus of the cured resin at 165° C. is 10 MPa to 50 GPa.

[0018] <5> according to <1> ~ <4> The airtight structure according to any one of the preceding claims, wherein the linear expansion coefficient of the cured resin is 0 ppm / K to 100 ppm / K.

[0019] <6> according to <1> ~ <5> The airtight structure according to any one of the preceding claims, wherein a difference between a linear expansion coefficient of the cured resin and a linear expansion coefficient of the ALD layer is 0 ppm / K to 30 ppm / K.

[0020] <7> according to <1> ~ <6> The airtight structure according to any one of the preceding claims, wherein the airtight portion is formed by a first cover substrate, a second cover substrate, and a wall member that joins the first cover substrate and the second cover substrate and separates an inner side from an outer side of the airtight portion.

[0021] <8> according to <7> In the airtight structure, the wall member is made of metal.

[0022] <9> according to <7> In the airtight structure, the wall member is made of resin.

[0023] <10> according to <1> ~ <9> The airtight structure according to any one of the preceding claims, wherein the interior of the airtight portion is filled with an inert gas.

[0024] <11> according to <1> ~ <10> The airtight structure according to any one of the preceding claims, wherein the ALD layer contains Al 2 O 3 .

[0025] <12> A method for manufacturing an airtight structure includes: forming a curable resin composition layer by covering an edge portion of an airtight portion with a curable resin composition; curing the curable resin composition layer to form a base layer; and forming an ALD layer covering the base layer.

[0026] <13> according to <12> In the method for manufacturing an airtight structure, the curable resin composition has thermosetting properties.

[0027] <14> according to <12> or <13> In the method for manufacturing an airtight structure, the curable resin composition is a positive photosensitive resin composition.

[0028] <15> according to <12> ~ <14> A method for manufacturing an airtight structure according to any one of the preceding claims, wherein the airtight portion is formed by joining the top of the first side wall frame and the top of the second side wall frame using a first covering substrate having a first metal side wall frame provided on one surface and a second covering substrate having a second metal side wall frame provided on one surface.

[0029] <16> A base resin composition for airtightness maintenance, comprising a curable component.

[0030] <17> according to <16> The airtight-maintaining base resin composition is a positive photosensitive resin composition.

[0031] <18> according to <16> The airtight-maintaining base resin composition is a negative photosensitive resin composition.

[0032] Effects of the Invention

[0033] According to the present disclosure, an airtight structure having excellent airtightness and a method for producing the same can be provided. In addition, according to the present disclosure, an airtight-maintaining base resin composition used for producing an airtight structure having excellent airtightness can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1A It is a top view of the airtight structure 10 .

[0035] Figure 1B It is a cross-sectional view of the airtight structure 10 taken along line AA.

[0036] Figure 1C This is a cross-sectional view taken along line AA regarding another embodiment of the airtight structure 10 .

[0037] Figure 1D This is a cross-sectional view taken along line AA of another embodiment of the airtight structure 10 .

[0038] Figure 2A It is a top view of the airtight structure 30 .

[0039] Figure 2B It is a cross-sectional view of the airtight structure 30 taken along line BB.

[0040] Figure 3A It is a top view of the airtight structure 40 .

[0041] Figure 3B It is a cross-sectional view of the airtight structure 40 taken along line CC.

[0042] Figure 4A It is a top view of the airtight structure 50 .

[0043] Figure 4B It is a cross-sectional view of the airtight structure 50 taken along line DD. DETAILED DESCRIPTION

[0044] Hereinafter, the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, except for the cases specifically indicated, the constituent elements (including element steps, etc.) are not essential. The numerical values ​​and their ranges are also not limiting of the present disclosure.

[0045] In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved.

[0046] In the present disclosure, in a numerical range expressed using “to”, the numerical values ​​described before and after “to” are included as the minimum value and the maximum value, respectively.

[0047] In the numerical ranges described in stages in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages.

[0048] In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the multiple substances present in the composition.

[0049] In the present disclosure, the term “layer” or “film” includes not only a case where the layer or film is formed on the entire region when the region where the layer or film exists is observed, but also a case where the layer or film is formed on only a part of the region.

[0050] In the present disclosure, “(meth)acryloyl” refers to at least one of acryloyl and methacryloyl, and “(meth)acrylic acid” refers to at least one of acrylic acid and methacrylic acid.

[0051] In the present disclosure, the average thickness of a layer or film is a value obtained by measuring the thickness of five points of the target layer or film and giving the measured thickness as the arithmetic mean value.

[0052] The thickness of a layer or film can be measured using a micrometer or the like. In the present disclosure, when the thickness of a layer or film can be directly measured, it is measured using a micrometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it can be measured by observing a cross-section of the object to be measured using an electron microscope.

[0053] <Airtight Structure>

[0054] The airtight structure of the present disclosure includes an airtight portion, a base layer including a cured resin covering an edge portion of the airtight portion, and an ALD layer covering the base layer.

[0055] Hereinafter, embodiments of the airtight structure disclosed herein and embodiments of the method for manufacturing the airtight structure disclosed herein will be described in detail with reference to the accompanying drawings. Figure 1A 、 Figure 2A 、 Figure 3A and Figure 4A For the sake of clarity, the description of the ALD layer is omitted.

[0056] In the following description, the same or corresponding parts are denoted by the same reference numerals, and overlapping descriptions may be omitted. Furthermore, the dimensional ratios in the drawings are not limited to those shown in the drawings.

[0057] (First embodiment)

[0058] Figure 1A : is a top view showing the first embodiment of the airtight structure of the present disclosure. Figure 1B yes Figure 1A AA line cross-section diagram.

[0059] Figure 1Aand Figure 1B The airtight structure 10 shown has an airtight portion 18 formed by a first cover substrate 12, a second cover substrate 14, and a wall member 16 that joins the first cover substrate 12 and the second cover substrate 14. The wall member 16, together with the first cover substrate 12 and the second cover substrate 14, separates the inside and outside of the airtight portion 18 and is provided on the inside relative to the outer periphery of the second cover substrate 14.

[0060] By arranging the wall member 16 on the inner side compared to the outer periphery of the second cover substrate 14 , a region A where the second cover substrate 14 covers the first cover substrate 12 is created.

[0061] The wall member 16 is formed, for example, by joining the top of a first metal side wall frame 20 provided on one surface of the first cover substrate 12 to the top of a second metal side wall frame 22 provided on one surface of the second cover substrate 14. Examples of methods for joining the top of the first side wall frame 20 and the top of the second side wall frame 22 include metal bonding, surface activation bonding, anodic bonding, and thermal diffusion bonding.

[0062] When the first side wall frame 20 and the second side wall frame 22 are made of metal, examples of the metal constituting the first side wall frame 20 and the second side wall frame 22 include Au, Cu, Sn-Cu alloy, Sn-Ag alloy, etc. Alternatively, the metal constituting the first side wall frame 20 and the second side wall frame 22 may be both Cu or Au, and Cu-Cu bonding or Au-Au bonding may be performed.

[0063] By making the first side-wall frame 20 and the second side-wall frame 22 into metal, the wall member 16 made of metal can be obtained.

[0064] In another way, Figure 1C As shown, the wall member 16 can also be formed by bringing the top of a third side wall frame 24 made of resin, which is provided on one surface of the first cover substrate 12, into contact with one surface of the second cover substrate 14, and then, as needed, bonding the top of the third side wall frame 24 to one surface of the second cover substrate 14 by heating and pressurizing. By making the side wall frame 24 from resin, the wall member 16 made of resin can be obtained. Examples of the resin constituting the third side wall frame 24 include polyimide resin, polyamide-imide resin, polybenzoxazole resin, epoxy resin, (meth)acrylic resin, and olefin resin.

[0065] If the resin can be given photosensitivity, desirable effects such as improved pattern formation and reduced processing volume (interval time between each process) can be achieved. Therefore, it is preferred that the resin contain a reactive functional group. Examples of the reactive functional group include amino, amide, imide, hydroxyl, aldehyde, ketone, carboxyl, (meth)acryloyl, ester, ether, alkenyl, and alkynyl groups.

[0066] Furthermore, in order to impart photosensitivity, the resin may contain a photopolymerization initiator or the like.

[0067] The thickness of the wall member 16 is appropriately set depending on the application of the airtight structure, and may be, for example, 1 μm to 50 μm.

[0068] The first covering substrate 12 and the second covering substrate 14 can include metal substrates such as copper and Al, SiC substrates, sapphire substrates, GaN substrates, piezoelectric substrates (lithium tantalate, lithium niobate, etc.), GaAs substrates, CdTe substrates, silicon substrates, germanium substrates, silicon nitride substrates and other semiconductor substrates, soda glass substrates, alkali-free glass substrates, low-expansion glass substrates, quartz glass substrates and other glass substrates, plastic substrates such as polyethylene terephthalate, etc.

[0069] The average thickness of the first cover substrate 12 and the second cover substrate 14 is appropriately set according to the application of the airtight structure, and can be, for example, 5 μm to 1.1 mm independently of each other.

[0070] The distance between the first cover substrate 12 and the second cover substrate 14 (ie, the height of the wall member 16 ) is appropriately set depending on the application of the airtight structure, and may be, for example, 5 μm to 500 μm.

[0071] The outer periphery of the airtight portion 18 is covered with a base layer 26 containing a cured resin. Covering the outer periphery of the airtight portion 18 with the base layer 26 improves the airtightness of the airtight portion 18 compared to when the airtight portion 18 is covered only with an ALD layer 28 described later.

[0072] The cross section of the corner portion B of the base layer 26 covering the periphery of the second cover substrate 14 is substantially a right angle. Figure 1D As shown, the corner portion B may be chamfered in cross section. If the corner portion B is chamfered, the coverage of the ALD layer 28 formed on the base layer 26, described later, at the corner portion B is easily improved, making it easier to ensure airtightness.

[0073] From the viewpoint of suppressing degradation in the heating step during mounting, the 5% weight loss temperature of the cured resin contained in the base layer 26 is mainly assumed to be 250°C to 400°C, preferably 300°C to 350°C.

[0074] The 5% weight loss temperature of the resin cured product can be measured as follows: using a differential thermal-thermogravimetric simultaneous measurement apparatus (for example, "TG / DTA7300" (product name, manufactured by Hitachi High-Technologies Corporation)), about 10 mg of sample is filled in a platinum pan (φ6 mm), and the temperature at which the weight loss rate of the sample reaches 5% compared to before heating is measured under a nitrogen flow of 100 mL / min and a heating rate of 10°C / min.

[0075] From the viewpoint of shape stability of the resin and the ALD layer, the storage elastic modulus of the cured resin contained in the base layer 26 at 165° C. is preferably 10 MPa to 50 GPa, more preferably 1 GPa to 10 GPa.

[0076] The storage modulus of a cured resin at 165°C can be determined by viscoelasticity measurement in tension mode using a dynamic viscoelasticity measuring instrument (e.g., RSAGII (manufactured by TA Instruments)). The storage modulus at 165°C is measured under the following measurement conditions: a heating rate of 10°C / min, a temperature range of 0°C to 300°C, a frequency of 10 Hz, and a strain of 0.1%.

[0077] From the viewpoint of shape stability against temperature changes, the glass transition temperature of the cured resin contained in the base layer 26 is preferably 150°C to 400°C, more preferably 150°C to 350°C, and even more preferably 250°C to 350°C.

[0078] The glass transition temperature of a cured resin is a value measured as follows.

[0079] For a 20 mm × 4 mm × 4 mm test piece, a thermomechanical analyzer (e.g., TAS-1000S manufactured by Rigaku Corporation) is used to measure the dimensional change in the longitudinal direction (linear expansion coefficient) of the test piece at a heating rate of 5°C / min. The temperature corresponding to the inflection point of the resulting thermal expansion curve is taken as the glass transition temperature.

[0080] From the perspective of thermal stress, the linear expansion coefficient of the cured resin contained in base layer 26 is preferably close to that of the substrate material and the material forming the hollow structure, preferably 0 ppm / K to 100 ppm / K, and more preferably 0 ppm / K to 25 ppm / K. In this disclosure, the linear expansion coefficient of the cured resin refers to the linear expansion coefficient in the temperature range equal to or less than the glass transition temperature of the cured resin.

[0081] The linear expansion coefficient of a cured resin is a value measured as follows.

[0082] Based on the measurement result of the linear expansion coefficient obtained in the measurement of the glass transition temperature, the linear expansion coefficient in the temperature range equal to or lower than the glass transition temperature can be obtained.

[0083] From the viewpoint of thermal stress, the difference between the linear expansion coefficient of the cured resin and the linear expansion coefficient of the ALD layer is preferably 0 ppm / K to 30 ppm / K, and more preferably 0 ppm / K to 20 ppm / K.

[0084] Examples of the cured resin contained in the base layer 26 include polyimide, polyamideimide, polybenzoxazole, epoxy resin, (meth)acrylic resin, polyolefin, polyamide, polyhydroxystyrene, norbornene resin, and novolac resin.

[0085] If the resin can be given photosensitivity, desirable effects such as improved pattern formation and reduced processing volume (interval time between each process) can be achieved. Therefore, it is preferred that the resin contain a reactive functional group. Examples of the reactive functional group include amino, amide, imide, hydroxyl, aldehyde, ketone, carboxyl, (meth)acryloyl, ester, ether, alkenyl, and alkynyl groups.

[0086] Furthermore, in order to impart photosensitivity, the resin may contain a photopolymerization initiator or the like.

[0087] The base layer 26 only needs to be thick enough to cover the outer peripheral edge of the airtight portion 18 .

[0088] The thickness of the base layer 26 in the thickness direction of the first cover substrate 12 (or the second cover substrate 14 ) may be set to be thicker than the height of the wall member 16 .

[0089] The thickness of the base layer 26 in the plane direction of the second cover substrate 14 only needs to be sufficient to cover the edge of the second cover substrate 14. By covering the edge of the second cover substrate 14 with the base layer 26, the uneven shape originating from the edge of the second cover substrate 14 can be smoothed. As a result, the coverage rate of the ALD layer 28 provided on the base layer 26 is easily improved. It should be noted that the thickness of the base layer 26 in the plane direction of the second cover substrate 14 refers to the thickness from the edge of the second cover substrate 14.

[0090] The base layer 26 is covered with the ALD layer 28. That is, the airtight portion 18 is doubly covered with the base layer 26 and the ALD layer 28. Therefore, in the airtight structure of the present disclosure, the airtight portion 18 has excellent airtightness.

[0091] By providing the base layer 26 below the ALD layer 28 and providing the ALD layer 28 after smoothing the base on which the ALD layer 28 is formed, the airtightness of the airtight portion 18 can be ensured even if the ALD layer 28 is a thin film. As a result, the reliability of the airtight structure is improved. In addition, by combining the base layer 26 and the ALD layer 28, it is not necessary to form an ALD layer 28 several μm thick to ensure airtightness. Compared to the case where only the ALD layer 28 is used, the airtightness of the airtight portion 18 can be ensured by the thin ALD layer 28 (for example, less than or equal to 1 μm), thereby improving the productivity of the airtight structure.

[0092] The components contained in the ALD layer 28 are not particularly limited, and examples thereof include SiO2, TiO2, Al2O3, ZrO2, TaN, TiN, SiN, ZnO, Ta2O5, etc. Among them, Al2O3 or SiN is preferred, and Al2O3 is more preferred.

[0093] The average thickness of the ALD layer 28 is not particularly limited as long as it is thick enough to cover the base layer 26 , and may be, for example, 1 nm to 1 μm.

[0094] A structure (not shown) is housed in the airtight portion 18. Examples of the structure include comb-shaped electrodes in MEMS, high-frequency devices, and pressure sensors. In particular, the airtight structure of the present disclosure is effective in improving the reliability of high-frequency devices.

[0095] The interior of the airtight portion 18 may be filled with air or an inert gas such as argon or nitrogen. The interior of the airtight portion 18 may be in a vacuum state equal to or less than atmospheric pressure.

[0096] (Second embodiment)

[0097] Figure 2A : is a top view showing a second embodiment of the airtight structure of the present disclosure. Figure 2B yes Figure 2A BB line cross-section diagram.

[0098] Figure 2A and Figure 2B The airtight structure 30 shown has an airtight portion 18 formed by a first cover substrate 12, a second cover substrate 14, and a wall member 16 that joins the first cover substrate 12 and the second cover substrate 14. The wall member 16 is provided at the periphery of the second cover substrate 14. Therefore, compared to the airtight structure 10, the area A where the second cover substrate 14 covers the first cover substrate 12 is not generated.

[0099] Details of the first cover substrate 12 , the second cover substrate 14 , the wall member 16 , the airtight portion 18 , the ALD layer 28 , and the base layer 26 constituting the airtight structure 30 are the same as those of the airtight structure 10 .

[0100] (Third embodiment)

[0101] Figure 3A : is a top view showing a third embodiment of the airtight structure of the present disclosure. Figure 3B yes Figure 3A CC line cross-section diagram.

[0102] Figure 3A and Figure 3B The airtight structure 40 shown has: a first covering substrate 12; a second covering substrate 14; a wide rib 42 made of resin, which is arranged between the first covering substrate 12 and the second covering substrate 14, constitutes the airtight portion 18, and covers the outer periphery of the airtight portion 18; and an ALD layer 28, which covers the first covering substrate 12, the second covering substrate 14 and the wide rib 42.

[0103] like Figure 3B As shown, the wide rib 42 is provided to extend from the inner side (the side where the airtight portion 18 is present) of the outer periphery of the second cover substrate 14 to the outer side.

[0104] Examples of the resin constituting the wide rib 42 include polyimide resin, polyamide-imide resin, polybenzoxazole resin, epoxy resin, (meth)acrylic resin, and olefin resin.

[0105] If the resin can be given photosensitivity, desirable effects such as improved pattern formation and reduced processing volume (interval time of the process) can be achieved. Therefore, it is preferred that the resin contain a reactive functional group. Examples of the reactive functional group include amino, amide, imide, hydroxyl, aldehyde, ketone, carboxyl, (meth)acryloyl, ester, ether, alkenyl, and alkynyl groups.

[0106] Furthermore, in order to impart photosensitivity, the resin may contain a photopolymerization initiator or the like.

[0107] The average thickness of the wide ribs 42 is appropriately set depending on the purpose of the airtight structure, and may be, for example, 1 μm to 150 μm.

[0108] Details of the first cover substrate 12 , the second cover substrate 14 , the airtight portion 18 , and the ALD layer 28 constituting the airtight structure 40 are the same as those of the airtight structure 10 .

[0109] (Fourth embodiment)

[0110] Figure 4A : is a top view showing a fourth embodiment of the airtight structure of the present disclosure. Figure 4B yes Figure 4A DD line cross-section diagram in.

[0111] Figure 4A and Figure 4B The airtight structure 50 shown has an airtight portion 18 formed by a first cover substrate 12, a second cover substrate 14, and a wall member 52 that joins the first cover substrate 12 and the second cover substrate 14. The wall member 52, together with the first cover substrate 12 and the second cover substrate 14, separates the inside and outside of the airtight portion 18 and is provided on the inside relative to the outer periphery of the second cover substrate 14.

[0112] The wall member 52 constituting the airtight structure 50 is configured to be taller in the thickness direction of the first cover substrate 12 (or the second cover substrate 14) than the wall member 16 constituting the airtight structure 10. Therefore, in the region C where the second cover substrate 14 covers the first cover substrate 12, the base layer 26 can be provided with a more uniform thickness on the surface of the wall member 52.

[0113] Details of the first cover substrate 12 , the second cover substrate 14 , the airtight portion 18 , the ALD layer 28 , and the base layer 26 constituting the airtight structure 50 are the same as those of the airtight structure 10 .

[0114] In the airtight structure 50, the wall member 52 can be made of resin or metal. Furthermore, the height of the wall member 52 is not particularly limited, as long as the base layer 26 is formed on the surface of the wall member 52. Furthermore, the thickness of the wall member 52 is not particularly limited, as long as it can maintain the structure of the wall member 52.

[0115] While the airtight structure of the present disclosure has been described above based on the first to fourth embodiments, the airtight structure of the present disclosure is not limited to the above configurations. For example, in the above embodiments, the airtight portion 18 has a hollow structure, but the airtight portion 18 may also have a solid structure, such as an optical waveguide constituting an optical waveguide element.

[0116] The airtight structure disclosed herein has excellent airtightness because the edge of the airtight portion is covered by a base layer containing a cured resin, which is further covered by an ALD layer. Furthermore, the improved airtightness of the airtight portion improves thermal reliability.

[0117] Furthermore, in the airtight structure of the present disclosure, since the ALD layer is formed on the base layer, the number of corner portions where stress is likely to concentrate is reduced, thereby improving mechanical reliability.

[0118] <Method for Manufacturing Airtight Structure>

[0119] The method for producing the airtight structure of the present disclosure is not particularly limited, and the airtight structure of the present disclosure can be produced by combining various known methods.

[0120] In order to simply manufacture the airtight structure of the present invention with excellent airtightness, the manufacturing method of the airtight structure of the present invention (hereinafter sometimes referred to as the manufacturing method of the present invention) may include: forming a curable resin composition layer by covering the edge portion of the airtight portion with a curable resin composition; curing the curable resin composition layer to form a base layer; and forming an ALD layer covering the base layer.

[0121] Hereinafter, each step of the production method of the present disclosure will be described.

[0122] In the production method of the present disclosure, the edge portion of the airtight portion is covered with the curable resin composition to form a curable resin composition layer.

[0123] The type of the airtight portion is not particularly limited, and as described above, it may be a hollow structure or a solid structure.

[0124] The curable resin composition layer can be formed by, for example, using a liquid curable resin composition and applying the curable resin composition by a known coating method so as to cover the edge of the airtight portion.

[0125] Examples of the coating method for the curable resin composition include knife coating, roll coating, spray coating, gravure coating, rod coating, curtain coating, blade coating, doctor coating, spin coating, screen printing, and inkjet coating. The curable resin composition layer can be formed using a lamination method using a film resist, a resin CVD method, and the like.

[0126] When the curable resin composition contains a solvent, at least a portion of the solvent can be removed from the curable resin composition by subjecting the curable resin composition layer to a drying treatment. Examples of the drying treatment include heat drying under normal pressure or reduced pressure, natural drying, and freeze drying.

[0127] The base layer is formed by curing the curable resin composition layer. The curing conditions and curing method of the curable resin composition layer are not particularly limited and can be appropriately selected according to the type of curable component contained in the curable resin composition.

[0128] When the curable resin composition has thermosetting properties, the curable resin composition layer can be cured by heating the curable resin composition layer to form a base layer. The heating temperature, heating conditions, etc. for curing the curable resin composition layer can be appropriately selected. In addition, when the curable resin composition has photocuring properties, the curable resin composition layer can be cured by irradiating the curable resin composition layer with light to form a base layer. The exposure amount, etc. for curing the curable resin composition layer can be appropriately set.

[0129] In order to form the base layer at the desired location, a positive photosensitive resin composition or a negative photosensitive resin composition can be used as the curable resin composition. Figure 1B In the case of a structure where the second cover substrate 14 covers the first cover substrate 12, as in the illustrated region A, the curable resin composition present in region A tends to remain unexposed when light is irradiated from the second cover substrate 14 side. Therefore, in an airtight structure having region A, it is preferable to use a positive-type photosensitive resin composition to prevent the unexposed portion of the curable resin composition from being removed by development. On the other hand, in the case of an airtight structure without region A, either a positive-type photosensitive resin composition or a negative-type photosensitive resin composition can be used.

[0130] A positive photosensitive resin composition or a negative photosensitive resin composition is used to form a curable resin composition layer, the curable resin composition layer is pattern-exposed, and developed using a developer to impart a desired resin pattern to the curable resin composition layer, thereby making a patterned resin film. Subsequently, the patterned resin film is heat-treated, thereby forming a base layer at a desired location.

[0131] The pattern exposure is performed by exposing to a predetermined pattern through a photomask, for example.

[0132] Examples of the active light to be irradiated include i-rays, broadband ultraviolet rays, visible rays, and radiation, with i-rays being preferred. Examples of the exposure apparatus include parallel exposure equipment, projection exposure equipment, stepper exposure equipment, and scanner exposure equipment.

[0133] By developing after exposure, a patterned resin film as a curable resin composition layer having a pattern formed thereon can be obtained. When the curable resin composition is a negative photosensitive resin composition, the unexposed portion is removed with a developer.

[0134] As the organic solvent used as the negative-type developer, a good solvent for the curable resin composition layer may be used alone, or a good solvent and a poor solvent may be appropriately mixed and used.

[0135] Examples of the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, cyclopentanone, cyclohexanone, and cycloheptanone.

[0136] Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0137] When the curable resin composition is a positive photosensitive resin composition, the exposed portion is removed with a developer.

[0138] Examples of the solution used as the positive-type developer include a tetramethylammonium hydroxide (TMAH) solution and a sodium carbonate solution.

[0139] The negative-type developer or the positive-type developer may contain a surfactant. The content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the developer.

[0140] The development time can be set to, for example, twice the time required for immersing the curable resin composition layer in the developer until the curable resin composition layer is completely dissolved.

[0141] The development time can be adjusted according to the components contained in the curable resin composition layer, and is, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0142] The developed patterned resin film may also be cleaned with a rinse solution.

[0143] As the rinse liquid, distilled water, methanol, ethanol, isopropyl alcohol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in appropriate mixtures. Furthermore, these can also be used in combination in stages.

[0144] By heating the patterned resin film, a patterned base layer is formed at a desired location. The heating temperature and heating conditions of the patterned resin film can be appropriately selected.

[0145] The base layer can be formed by applying a curable resin composition to a portion of the edge portion of the airtight portion where the base layer is required, and then curing the curable resin composition by heating or light irradiation.

[0146] The method for applying the curable resin composition to the portion requiring the base layer is not particularly limited, and conventionally known methods can be employed. Examples of the method for applying the curable resin composition to the portion requiring the base layer include lamination using a film resist, resin CVD, inkjet, screen printing using a screen mask with openings in the portion requiring the base layer, and stamping.

[0147] Alternatively, after forming a base layer using a curable resin composition to cover the entire surface of the airtight portion, the unnecessary base layer may be removed by dry etching, wet etching, ion milling, dicing, or peeling after resin vapor deposition, thereby forming a base layer at a desired location.

[0148] An ALD layer is formed on the base layer so as to cover the base layer.

[0149] ALD is a method that deposits atomic layers one by one by sequentially introducing a source gas and a reducing gas while purging. The types of source gas and reducing gas are appropriately selected based on the components of the ALD layer to be formed. For example, when the ALD layer contains Al2O3, trimethylaluminum and water can be used as the source gas and reducing gas, respectively.

[0150] The various conditions for forming the ALD layer, such as gas flow rate, temperature conditions, gas supply time, substrate temperature, and chamber pressure, are appropriately set in consideration of the components contained in the formed ALD layer, the average thickness of the ALD layer, and the like.

[0151] It should be noted that in the manufacturing method disclosed herein, in order to prevent cracks from occurring in the ALD layer through a thermal history due to the difference in linear expansion coefficient between the ALD layer and the base layer, the temperature of the base layer when forming the ALD layer may be greater than or equal to 125°C. Generally, the ceramic constituting the ALD layer has a tendency to be strong in resistance to compressive loads but weak in resistance to tensile loads. By forming the ALD layer in a state where the base layer is heated to a temperature greater than or equal to 125°C, the ALD layer also maintains a contracted state as the base layer contracts due to a decrease in the temperature of the base layer. By maintaining the contracted state of the ALD layer, when the base layer expands due to another increase in temperature, the tensile load applied to the ALD layer is easily reduced, and cracks are less likely to occur in the ALD layer. Therefore, the reliability of the airtight structure is easily improved.

[0152] Note that, in order to suppress thermal degradation of the airtight structure, the temperature of the base layer during the formation of the ALD layer may be 350° C. or lower.

[0153] In the disclosed method, an ALD layer is formed on a base layer, covering the base layer. The base layer and the ALD layer together ensure the airtightness of the airtight portion. Therefore, compared to a case where the ALD layer alone ensures the airtightness of the airtight portion, the ALD layer can be made thinner. Consequently, the ALD layer deposition time can be shortened.

[0154] The airtight structure of the present disclosure is manufactured through the above steps. According to the manufacturing method of the present disclosure, the reliability of the airtight structure can be improved, and the formation time of the ALD layer can be shortened.

[0155] The production method of the present disclosure may include other steps besides the above-mentioned steps.

[0156] In the present disclosure, the airtight portion may be formed by any method, and the manufacturing method thereof is not particularly limited.

[0157] The airtight portion can be formed by using Figure 1B The first cover substrate 12 shown has a first metal side wall frame 20 on one surface, and the second cover substrate 14 has a second metal side wall frame 22 on one surface. The top of the first side wall frame 20 is joined to the top of the second metal side wall frame 22 .

[0158] The method for joining the top of the first side-wall frame 20 and the top of the metal second side-wall frame 22 is not particularly limited, and methods such as metal bonding, surface activation bonding, anodic bonding, and thermal diffusion bonding may be used.

[0159] The manufacturing apparatus used to implement the method of the present invention is not particularly limited. The method of the present invention can be implemented using multiple apparatuses, such as a coating apparatus for applying a curable resin composition in a manner that covers the edge of the airtight portion, a dryer for removing at least a portion of the solvent from the curable resin composition, a curing apparatus for curing the curable resin composition layer into a pattern through exposure, development, heating, etc., and a film-forming apparatus for forming an ALD layer. In addition, a manufacturing apparatus comprising a coating unit, a drying unit, a curing unit, and a film-forming unit can be used to implement the method of the present invention in a single apparatus.

[0160] <Airtightness-maintaining base resin composition>

[0161] The airtightness-maintaining base resin composition disclosed herein (hereinafter sometimes referred to as the composition disclosed herein) contains a curable component. The composition disclosed herein may be a positive-type photosensitive resin composition or a negative-type photosensitive resin composition. Furthermore, the composition disclosed herein may be a thermosetting resin composition or a photocurable resin composition that is not developable.

[0162] In this disclosure, a "curable component" refers to a component that exhibits the property of curing by exposure to light or heating. A curable component may cure by exposure to light or heating, or may cure by the action of an acid component or free radical component generated by an acid generator, free radical polymerization initiator, or the like.

[0163] The cured resin contained in the base layer constituting the airtight structure may be a cured product of the composition disclosed herein.

[0164] Hereinafter, the composition of the present disclosure will be described in detail, taking as an example a case where the composition of the present disclosure is a positive photosensitive resin composition.

[0165] The positive photosensitive resin composition may include (A) an alkali-soluble resin, (B) a thermosetting resin, and (C) a photosensitizer.

[0166] ((A) component: alkali-soluble resin)

[0167] The alkali-soluble resin is not particularly limited, but preferably has high electrical insulation properties, and examples thereof include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, polyamideimide, polyhydroxystyrene, novolac resin, norbornene resin, epoxy resin, and (meth)acrylic resin.

[0168] In particular, from the viewpoint of achieving both insulation and mechanical properties, the alkali-soluble resin is preferably polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, a novolac resin, or polyhydroxystyrene, and more preferably at least one of a polyimide precursor and a polybenzoxazole precursor.

[0169] Alkali-soluble resins are usually developed with an aqueous alkaline solution. Therefore, they are preferably soluble in an aqueous alkaline solution.

[0170] As the alkaline aqueous solution, organic ammonium aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution, metal hydroxide aqueous solutions, carbonate aqueous solutions, organic amine aqueous solutions, etc. can be listed. Usually, a TMAH aqueous solution having a concentration of 2.38% by mass is preferably used. Therefore, component (A) is preferably soluble in a TMAH aqueous solution.

[0171] It should be noted that the following description is a benchmark for component (A) being soluble in an alkaline aqueous solution. Component (A) is dissolved in any solvent to form a solution, and then spin-coated on a substrate such as a silicon wafer to form a resin film having a film thickness of about 5 μm. This is then immersed in any one of a TMAH aqueous solution, a metal hydroxide aqueous solution, a carbonate aqueous solution, and an organic amine aqueous solution at 20° C. to 25° C. When the result dissolves to form a solution, it is determined that component (A) used is soluble in an alkaline aqueous solution.

[0172] The molecular weight of the component (A) is not particularly limited, but is preferably, for example, 10,000 to 200,000, more preferably 12,000 to 100,000 in terms of weight average molecular weight.

[0173] The weight average molecular weight can be measured by gel permeation chromatography and can be determined by conversion using a standard polystyrene calibration curve.

[0174] The dispersion degree obtained by dividing the weight average molecular weight by the number average molecular weight is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.

[0175] -Polyimide precursor-

[0176] The polyimide precursor is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Polyamic acid ester and polyamic acid amide are compounds in which the hydrogen atoms of at least some of the carboxyl groups in polyamic acid are substituted with monovalent organic groups. Polyamic acid salt is a compound in which at least some of the carboxyl groups in polyamic acid form a salt structure with a basic compound having a pH of 7 or greater.

[0177] The polyimide precursor may contain a compound having a structural unit represented by the following general formula (I).

[0178] [Chemistry 1]

[0179]

[0180] In the general formula (I), X represents a tetravalent organic group, and Y represents a divalent organic group. 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them may have a polymerizable unsaturated bond.

[0181] The polyimide precursor may have a plurality of structural units represented by the general formula (I), wherein X, Y, R 6 and R 7 They can be the same or different.

[0182] It should be noted that R 6 and R 7 As long as each is independently a hydrogen atom or a monovalent organic group, the combination thereof is not particularly limited. 6 and R 7In the above, at least one of them may be a hydrogen atom and the rest may be monovalent organic groups described below, or they may all be the same or different monovalent organic groups, or both of them may be hydrogen atoms. As described above, when the polyimide precursor has a plurality of structural units represented by the above general formula (I), R 6 and R 7 The combinations can be the same or different.

[0183] In the general formula (I), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms.

[0184] From the viewpoint of heat resistance, the tetravalent organic group represented by X may include an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (e.g., carbon atoms constituting the aromatic ring are 6 to 20), aromatic heterocyclic groups (e.g., atoms constituting the heterocyclic ring are 5 to 20), and the like. The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring.

[0185] When the tetravalent organic group represented by X includes an aromatic ring, each aromatic ring may or may not have a substituent. Examples of the substituent of the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group.

[0186] When the tetravalent organic group represented by X includes a benzene ring, the tetravalent organic group represented by X preferably includes 1 to 4 benzene rings, more preferably includes 1 to 3 benzene rings, and even more preferably includes 1 or 2 benzene rings.

[0187] In the case where the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be connected by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), a silicon bond (-Si(R A )2-; 2 R A Each independently represents a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (-O-(Si(R B )2-O-) n ; 2 R B Each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer greater than or equal to 1. ) or a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings may be bonded at two locations via a single bond and at least one of the linking groups to form a 5-membered or 6-membered ring containing the linking group between the two benzene rings.

[0188] In general formula (I), -COOR 6The -COOR group and the -CONH- group are preferably located in ortho positions relative to each other. 7 The -CO- group and the -CO- group are preferably located in ortho positions relative to each other.

[0189] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulas (A) to (F). Among them, from the viewpoint of obtaining a base layer with excellent flexibility, a group represented by the following formula (E) is preferred, a group represented by the following formula (E) in which C is an ether bond is more preferred, and an ether bond is even more preferred.

[0190] It should be noted that the present disclosure is not limited to the following specific examples.

[0191] [Chemistry 2]

[0192]

[0193] In formula (D), A and B are each independently a single bond or a divalent group not conjugated with the benzene ring. However, it is not possible for both A and B to be single bonds. Examples of the divalent group not conjugated with the benzene ring include methylene, halomethylene, halogenated methylmethylene, carbonyl, sulfonyl, ether bond (-O-), thioether bond (-S-), silicon bond (-Si(R A )2-; 2 R A Each independently represents a hydrogen atom, an alkyl group or a phenyl group. ) etc. Among them, A and B are each independently preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a thioether bond, etc., and more preferably an ether bond.

[0194] In formula (E), C represents an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), a phenylene group, an ester bond (-OC(=O)-), a silicon bond (-Si(R A )2-; 2 R A Each independently represents a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (-O-(Si(R B )2-O-) n ; 2 R B Each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or greater than or equal to 2. ) or a divalent group formed by combining at least two of them. C preferably contains an ether bond, preferably an ether bond.

[0195] Furthermore, C may be a structure represented by the following formula (C1).

[0196] [Chemistry 3]

[0197]

[0198] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an alkylene group having 1 or 2 carbon atoms.

[0199] Specific examples of the alkylene group represented by C in formula (E) include straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene, methylethylene, ethylmethylene, dimethylmethylene, 1,1-dimethylethylene, 1-methyltrimethylene, 2-methyltrimethylene, ethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltrimethylene, 2-ethyltrimethylene, 1,1 - Branched chain alkylene groups such as dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene. Among them, methylene is preferred.

[0200] The haloalkylene group represented by C in formula (E) is preferably a haloalkylene group having 1 to 10 carbon atoms, more preferably a haloalkylene group having 1 to 5 carbon atoms, and still more preferably a haloalkylene group having 1 to 3 carbon atoms.

[0201] Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in formula (E) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene, difluoromethylene, hexafluorodimethylmethylene, and the like are preferred.

[0202] As R contained in the above silicon bond or siloxane bond A or R B The alkyl group represented by is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably an alkyl group having 1 or 2 carbon atoms. A or R B Specific examples of the alkyl group represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.

[0203] Specific examples of the tetravalent organic group represented by X may be groups represented by the following formulas (J) to (O).

[0204] [Chemistry 4]

[0205]

[0206] From the viewpoint of adjusting the thermal expansion coefficient of the substrate, the tetravalent organic group represented by X may include an alicyclic ring. In the case where the tetravalent organic group represented by X includes an alicyclic ring, ring structures containing no unsaturated bonds such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a decalin ring, a norbornane ring, an adamantane ring, a bicyclo [2.2.2] octane ring, and ring structures containing unsaturated bonds such as a cyclohexene ring may be cited. In addition, spirocyclic structures containing these ring structures may also be cited. The alicyclic ring may have substituents such as an oxo group (=O), an alkyl group, a fluorine atom, a haloalkyl group, a hydroxyl group, an amino group, or may be unsubstituted.

[0207] Specific examples of the case where the tetravalent organic group represented by X has a spiro structure include the following formula (P).

[0208] [Chemistry 5]

[0209]

[0210] In the general formula (I), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms.

[0211] The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bonding positions are substituted by atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups) by the tetravalent organic group represented by X.

[0212] The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of the divalent aromatic group include a divalent aromatic hydrocarbon group (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), a divalent aromatic heterocyclic group (for example, the number of atoms constituting the heterocyclic ring is 5 to 20), and the like, preferably a divalent aromatic hydrocarbon group.

[0213] In addition, an aromatic group refers to a group containing an aromatic ring.

[0214] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formulas (G) to (H). Among them, from the viewpoint of obtaining a base layer with excellent flexibility, a group represented by the following formula (H) is preferred, a group represented by the following formula (H) in which D is a single bond or an ether bond is more preferred, and a single bond or an ether bond is even more preferred.

[0215] [Chemistry 6]

[0216]

[0217] In formulae (G) to (H), R each independently represents an alkyl group, an alkoxy group, a hydroxyl group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents an integer of 0 to 4.

[0218] In formula (H), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), a phenylene group, an ester bond (-OC(=O)-), a silicon bond (-Si(R A )2-; 2 R A Each independently represents a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (-O-(Si(R B )2-O-) n ; 2 R B Each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer greater than or equal to 1 or 2. ) or a divalent group formed by combining at least two of them. In addition, D can be a structure represented by the above formula (C1). The specific example of D in formula (H) can be a single bond, or the same as the specific example of C in formula (E).

[0219] D in formula (H) is preferably each independently a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, or the like.

[0220] The alkyl group represented by R in formula (G) to formula (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 or 2 carbon atoms.

[0221] Specific examples of the alkyl group represented by R in formula (G) to formula (H) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0222] The alkoxy group represented by R in formula (G) to formula (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and still more preferably an alkoxy group having 1 or 2 carbon atoms.

[0223] Specific examples of the alkoxy group represented by R in formula (G) to formula (H) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy.

[0224] The haloalkyl group represented by R in formula (G) to formula (H) is preferably a haloalkyl group having 1 to 5 carbon atoms, more preferably a haloalkyl group having 1 to 3 carbon atoms, and still more preferably a haloalkyl group having 1 or 2 carbon atoms.

[0225] Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among them, fluoromethyl, difluoromethyl, trifluoromethyl, etc. are preferred.

[0226] In formulae (G) to (H), n is each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0227] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, and a divalent group having a polyalkylene oxide structure.

[0228] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and still more preferably an alkylene group having 1 to 10 carbon atoms.

[0229] Specific examples of the alkylene group represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonamethylene, and 2-methyldecamethylene.

[0230] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms.

[0231] Specific examples of the cycloalkylene group represented by Y include cyclopropylene group and cyclohexylene group.

[0232] The unit structure contained in the bivalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among these, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one or two or more.

[0233] The divalent organic group represented by Y may also be a divalent group having a polysiloxane structure. Examples of the divalent group having a polysiloxane structure represented by Y include a divalent group having a polysiloxane structure in which a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

[0234] Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl. Among them, methyl is preferred.

[0235] The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted. Specific examples of the substituents in the case of aryl groups include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl, naphthyl, and benzyl groups. Phenyl groups are preferred.

[0236] The number of the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one or two or more.

[0237] The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in the general formula (I) via an alkylene group such as a methylene group or an ethylene group, an arylene group such as a phenylene group, or the like.

[0238] The group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H'), formula (H"), or formula (H'").

[0239] [Chemistry 7]

[0240]

[0241] In formula (H'"), R each independently represents an alkyl group, an alkoxy group, a haloalkyl group, a phenyl group, a hydroxyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0242] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (I) is not particularly limited. Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include a combination in which X is a group represented by formula (E) and Y is a group represented by formula (H).

[0243] R 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aliphatic hydrocarbon group having 1 to 4 carbon atoms and an organic group having an unsaturated double bond.

[0244] Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. Among them, an ethyl group, an isobutyl group, and a tert-butyl group are preferred.

[0245] The content of the structural unit represented by the general formula (I) contained in the compound having the structural unit represented by the general formula (I) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more relative to all structural units. The upper limit of the above content is not particularly limited and may be 100 mol%.

[0246] The polyimide precursor can be a polyimide precursor synthesized using tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (I), X is equivalent to a residue derived from tetracarboxylic dianhydride, and Y is equivalent to a residue derived from a diamine compound. It should be noted that the polyimide precursor can also be a polyimide precursor synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[0247] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,5,6-naphthalene ... 4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexa Fluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and the like.

[0248] Tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0249] Specific examples of the diamine compound include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone ... ,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diamino-mesitylene, 1,5 -diaminonaphthalene, 4,4'-benzophenone diamine, bis{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6 -Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane, etc.

[0250] The diamine compounds may be used alone or in combination of two or more.

[0251] It has a structural unit represented by the general formula (I) and R in the general formula (I) 6 and R 7 The compound in which at least one of the components is a monovalent organic group can be obtained, for example, by the following method (a) or (b).

[0252] (a) Tetracarboxylic dianhydride (preferably tetracarboxylic dianhydride represented by the following general formula (I')) is reacted with a compound represented by R-OH in an organic solvent to produce a diester derivative, and then the diester derivative is subjected to a condensation reaction with a diamine compound represented by H2N-Y-NH2.

[0253] (b) Tetracarboxylic dianhydride and a diamine compound represented by H2N-Y-NH2 are reacted in an organic solvent to obtain a polyamic acid solution, and a compound represented by R-OH is added to the polyamic acid solution and reacted in an organic solvent to introduce an ester group.

[0254] Here, Y in the diamine compound represented by H2N-Y-NH2 is the same as Y in the general formula (I), and the specific examples and preferred examples are also the same. In addition, R in the compound represented by R-OH represents a monovalent organic group, and the specific examples and preferred examples are the same as R in the general formula (I). 6 and R 7 The same situation.

[0255] The tetracarboxylic dianhydride represented by general formula (I'), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH may be used alone or in combination of two or more.

[0256] Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropionamide. Among them, 3-methoxy-N,N-dimethylpropionamide is preferred.

[0257] A polyimide precursor can also be synthesized by reacting a dehydration condensation agent with the compound represented by R—OH on the polyamic acid solution. The dehydration condensation agent preferably includes at least one selected from the group consisting of trifluoroacetic anhydride, N,N′-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0258] The compound contained in the polyimide precursor can be obtained by allowing the compound represented by R-OH to act on the tetracarboxylic dianhydride represented by the following general formula (I') to prepare a diester derivative, then allowing a chlorinating agent such as thionyl chloride to act to convert it into an acid chloride, and then allowing the diamine compound represented by H2N-Y-NH2 to react with the acid chloride.

[0259] The compound contained in the polyimide precursor can be obtained by reacting a diamine compound represented by H2N-Y-NH2 with a tetracarboxylic dianhydride represented by the following general formula (I') to form a diester derivative, and then reacting the diester derivative with the diamine compound represented by H2N-Y-NH2 in the presence of a carbodiimide compound.

[0260] The compound contained in the polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (I') with a diamine compound represented by H2N-Y-NH2 to form a polyamic acid, then isimidizing the polyamic acid in the presence of a dehydrating condensation agent such as trifluoroacetic anhydride, and then reacting the compound represented by R-OH. Alternatively, the compound represented by R-OH can be allowed to act on a portion of the tetracarboxylic dianhydride in advance, and the partially esterified tetracarboxylic dianhydride can be reacted with the diamine compound represented by H2N-Y-NH2.

[0261] [Chemistry 8]

[0262]

[0263] In the general formula (I'), X is the same as X in the general formula (I), and the specific examples and preferred examples are also the same.

[0264] Examples of the compound represented by R—OH used in the synthesis of the compound contained in the polyimide precursor include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.

[0265] -Polybenzoxazole precursor-

[0266] The type of the polybenzoxazole precursor is not particularly limited. The polybenzoxazole precursor may preferably have a structural unit represented by the following formula (II).

[0267] [Chemistry 9]

[0268]

[0269] In formula (II), U is a tetravalent organic group, and V is a divalent organic group.

[0270] The amide unit containing a hydroxyl group in formula (II) is converted at least partially into an oxazole ring having excellent heat resistance, chemical resistance and electrical properties by dehydration ring closure in the heating step.

[0271] Furthermore, among the structural units represented by formula (II), the amide unit containing a hydroxyl group is effective in improving the solubility of the polymer in an alkaline aqueous solution.

[0272] The polymer having the structural unit represented by formula (II) may contain only one structural unit or two or more. In the case of a copolymer having two or more structural units, it may be a polymer having at least two structural units represented by formula (II) or a polymer having a structure represented by formula (III).

[0273] When a polymer having a structural unit represented by formula (II) has at least two structural units represented by formula (II), the combination of structural units represented by formula (II) is not particularly limited, and may be, for example, a structural unit in which the divalent organic group represented by V is a divalent aromatic group, and a structural unit in which V is a divalent organic group having an aliphatic structure and having 6 to 30 carbon atoms.

[0274] [Chemistry 10]

[0275]

[0276] In formula (III), U is a tetravalent organic group, and V and W are each independently a divalent organic group. j and k represent mole fractions, and when the sum of j and k is 100 mol%, j is 60 to 99.9 mol%, and k is 0.1 to 40 mol% (preferably j is 80 to 99.9 mol%, and k is 0.1 to 20 mol%).

[0277] In formulas (II) and (III), the tetravalent organic group represented by U is a residue of a diamine used in the synthesis of the polyhydroxyamide. The tetravalent organic group represented by U is preferably a tetravalent aromatic group or an organic group having 6 to 40 carbon atoms, more preferably a tetravalent aromatic group having 6 to 40 carbon atoms. The tetravalent aromatic group preferably has all four bonding sites on the aromatic ring.

[0278] Examples of diamines that provide a tetravalent organic group represented by U include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, but are not limited thereto.

[0279] The divalent organic group represented by W in formula (III) is a residue of a diamine used in the synthesis of the polyhydroxyamide. The divalent organic group represented by W is preferably a divalent aromatic group, a divalent aliphatic group, or an organic group having 4 to 20 carbon atoms, and more preferably an aromatic group having 4 to 20 carbon atoms. The divalent organic group represented by W is a residue of a diamine other than the diamine that provides the tetravalent organic group represented by U.

[0280] Examples of the diamines that provide a divalent organic group represented by W include aromatic diamine compounds such as 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, and 1,4-bis(4-aminophenoxy)benzene. Examples of the diamines having a silicone group include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E (all manufactured by Shin-Etsu Chemical Co., Ltd., trade names), but are not limited thereto.

[0281] In formulas (II) and (III), the divalent organic group represented by V is a residue of a dicarboxylic acid or a dicarboxylic acid derivative (hereinafter referred to as dicarboxylic acids) used in the synthesis of the polyhydroxyamide. The divalent organic group represented by V is preferably a divalent aromatic group or an organic group having 6 to 40 carbon atoms.

[0282] From the viewpoint of heat resistance, a divalent aromatic group having 6 to 40 carbon atoms is preferred, and as the divalent aromatic group, both bonding sites are preferably present on the aromatic ring.

[0283] From the viewpoint of high dehydration ring closure rate in a heating step at low temperature (eg, 200° C. or less) and good heat resistance and mechanical strength, V is preferably a divalent organic group having an aliphatic structure and 6 to 30 carbon atoms.

[0284] Examples of the dicarboxylic acid providing a divalent organic group represented by V include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether (4,4'-diphenylether dicarboxylic acid), 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5-tert-butylisophthalic acid, Aromatic dicarboxylic acids such as bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, and 2,6-naphthalene dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, malonic acid having an aliphatic straight-chain structure, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid Acid, dimethyl methyl succinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorodecaic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, decanedioic acid Tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, triundecanedioic acid, dotriaconedioic acid, diglycolic acid, and the like, and further examples include dicarboxylic acids represented by the following formulas, but are not limited thereto. These compounds can be used alone or in combination of two or more.

[0285] [Chemistry 11]

[0286]

[0287] In the formula, each Z is independently a hydrocarbon group having 1 to 6 carbon atoms, and i is an integer of 1 to 6.

[0288] In the present disclosure, the method for producing a polybenzoxazole precursor is not particularly limited. Generally, it can be synthesized by using dicarboxylic acids and hydroxyl-containing diamines, and, if necessary, diamines other than hydroxyl-containing diamines. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting it with a diamine. As the dihalide derivative, a dichloride derivative is preferred.

[0289] As a method for synthesizing dichloride derivatives, dicarboxylic acids can be reacted with a halogenating agent in a solvent, or reacted in an excess of a halogenating agent and then distilled to remove the excess. As halogenating agents, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are commonly used in carboxylic acid chlorination reactions, can be used. As reaction solvents, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, N,N-dimethylformamide, toluene, benzene, etc. can be used.

[0290] The amount of these halogenating agents used is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, per 1.0 mol of the dicarboxylic acid derivative when the reaction is carried out in a solvent. When the reaction is carried out in a halogenating agent, the amount is preferably 4.0 to 50 mol, more preferably 5.0 to 20 mol. The reaction temperature is preferably -10°C to 70°C, more preferably 0°C to 20°C.

[0291] The reaction of the dichloride derivative with the diamine is preferably carried out in an organic solvent in the presence of a dehydrohalogenation agent. Examples of dehydrohalogenation agents include organic bases such as pyridine and triethylamine. Examples of organic solvents include N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, and N,N-dimethylformamide. The reaction temperature is preferably -10°C to 30°C, more preferably 0°C to 20°C.

[0292] ((B) Thermosetting resin)

[0293] The positive-type photosensitive resin composition preferably contains (B) a thermosetting resin. Examples of the thermosetting resin (B) include acrylate resins, epoxy resins, cyanate resins, maleimide resins, allyl nadic imide resins, phenolic resins, urea resins, melamine resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, triallyl cyanurate resins, polyisocyanate resins, resins containing tris(2-hydroxyethyl)isocyanurate, resins containing triallyl trimellitate, and thermosetting resins synthesized from cyclopentadiene.

[0294] By adding a compound having a glycidyl group to the positive photosensitive resin composition, when the curable resin composition layer after pattern formation is heated and cured, it reacts with component (A) to form a cross-linked structure. This can prevent the brittleness and melting of the film. As the compound having a glycidyl group, conventionally known compounds can be used. Specific examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, glycidylamine, heterocyclic epoxy, polyalkylene glycol diglycidyl ether, etc.

[0295] The amount of such a compound having a glycidyl group when added is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, relative to 100 parts by mass of the component (A), from the viewpoint of solubility in an aqueous alkaline solution and physical properties of the cured film.

[0296] ((C) Photosensitizer)

[0297] The positive photosensitive resin composition preferably contains a photosensitizer (C). As the photosensitizer (C), a photoacid generator that generates an acid by light irradiation can be used.

[0298] The photoacid generator generates an acid by light irradiation, and has a function of increasing the solubility of the light-irradiated portion of the curable resin composition layer in an alkaline aqueous solution.

[0299] Examples of photoacid generators include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. These photoacid generators may be used alone or in combination of two or more, depending on the purpose and application. Among these, o-quinonediazide compounds are preferably used due to their high sensitivity.

[0300] As the o-quinonediazide compound, for example, one obtained by subjecting o-quinonediazidesulfonium chloride to a condensation reaction with a hydroxy compound and / or an amino compound in the presence of a dealkalizing agent can be used.

[0301] Examples of the o-quinonediazidesulfonium chloride used in the reaction include benzoquinone-1,2-diazide-4-sulfonium chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-6-sulfonyl chloride.

[0302] Examples of the hydroxy compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'- Tetrahydroxybenzophenone, 2,3,4,2',3'-pentahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, bis(2,3,4-trihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)propane, 4b,5,9b,10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno[2,1-a]indene, tris(4-hydroxyphenyl)methane, and tris(4-hydroxyphenyl)ethane.

[0303] Examples of the amino compound used in the reaction include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and bis(4-amino-3-hydroxyphenyl)hexafluoropropane.

[0304] Among them, from the viewpoint of reactivity when synthesizing an o-quinonediazide compound and from the viewpoint of an appropriate absorption wavelength range when exposing the curable resin composition layer, it is preferable to use a compound obtained by a condensation reaction of 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane and 1-naphthoquinone-2-diazide-5-sulfonyl chloride, or a compound obtained by a condensation reaction of tris(4-hydroxyphenyl)methane or tris(4-hydroxyphenyl)ethane and 1-naphthoquinone-2-diazide-5-sulfonyl chloride.

[0305] As the dehydrochlorination agent used in the reaction, for example, sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine and pyridine can be mentioned. In addition, as the reaction solvent, for example, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether and N-methyl-2-pyrrolidone can be used.

[0306] The o-quinonediazidesulfonyl chloride and the hydroxyl compound and / or amino compound are preferably blended such that the total number of moles of the hydroxyl group and the amino group is 0.5 to 1 mole per 1 mole of the o-quinonediazidesulfonyl chloride. The preferred blending ratio of the dehydrochlorination agent to the o-quinonediazidesulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95 molar equivalents.

[0307] It should be noted that the preferred reaction temperature for the above reaction is 0°C to 40°C, and the preferred reaction time is 1 hour to 10 hours.

[0308] From the perspective of increasing the difference in dissolution rate between the exposed and unexposed parts and improving sensitivity, the content of the photosensitive agent (C) is preferably 3 to 100 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, based on 100 parts by mass of the alkali-soluble resin (A).

[0309] (Low molecular weight compound having a phenolic hydroxyl group)

[0310] The positive photosensitive resin composition may contain a low-molecular compound having a phenolic hydroxyl group.

[0311] The low-molecular compound having a phenolic hydroxyl group is used to increase the dissolution rate of the exposed portion during development with an alkaline aqueous solution, thereby improving sensitivity. Furthermore, the inclusion of this component allows the component to react with component (A) to form a crosslinked structure when the patterned curable resin composition layer is heated and cured. This can prevent film brittleness and film melting.

[0312] The molecular weight of such a low molecular weight compound having a phenolic hydroxyl group is preferably 2000 or less. In consideration of solubility in aqueous alkaline solution and the balance between photosensitivity and cured film properties, the number average molecular weight is preferably 94 to 2000, more preferably 108 to 2000, and even more preferably 108 to 1500.

[0313] The amount of the low-molecular compound having a phenolic hydroxyl group is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 25 parts by mass relative to 100 parts by mass of component (A), from the perspectives of development time, the permissible range of the residual film rate in the unexposed portion, and the properties of the cured film.

[0314] (a compound that generates an acid when heated)

[0315] The positive photosensitive resin composition may contain a compound that generates an acid when heated.

[0316] By using this component, an acid is generated when the curable resin composition layer is heated, which promotes the reaction between component (A) and the compound having a glycidyl group or the low-molecular compound having a phenolic hydroxyl group, i.e., the thermal crosslinking reaction, thereby improving the heat resistance of the cured film. Furthermore, this component also generates acid upon light irradiation, thereby increasing the solubility of the exposed portion in an alkaline aqueous solution. Consequently, the difference in solubility between the unexposed portion and the exposed portion in an alkaline aqueous solution becomes further increased, thereby improving resolution.

[0317] Such a component preferably generates an acid by heating to, for example, 50° C. to 250° C. Specific examples of such a component include salts formed from a strong acid and a base, such as an onium salt, and imide sulfonate.

[0318] Examples of the onium salt include diaryl iodonium salts such as aryldiazonium salts and diphenyliodonium salts; di(alkylaryl)iodonium salts such as di(tert-butylphenyl)iodonium salts; trialkylsulfonium salts such as trimethylsulfonium salts; dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salts; diarylmonoalkylsulfonium salts such as diphenylmethylsulfonium salts; and triarylsulfonium salts. Among them, preferred are di(tert-butylphenyl)iodonium p-toluenesulfonic acid, di(tert-butylphenyl)iodonium trifluoromethanesulfonic acid, trimethylsulfonium trifluoromethanesulfonic acid, dimethylphenylsulfonium trifluoromethanesulfonic acid, diphenylmethylsulfonium trifluoromethanesulfonic acid, di(tert-butylphenyl)iodonium nonafluorobutanesulfonic acid, diphenyliodonium camphorsulfonic acid, diphenyliodonium ethanesulfonic acid, dimethylphenylsulfonium benzenesulfonic acid, and diphenylmethylsulfonium toluenesulfonic acid.

[0319] In addition to the above-mentioned onium salts, salts formed from strong acids and bases, such as pyridinium salts, can also be used as salts formed from strong acids and bases. Examples of strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. Examples of bases include pyridine, alkylpyridines such as 2,4,6-collidine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated N-alkylpyridines.

[0320] As the imide sulfonate, for example, naphthylimide sulfonate and phthalimide sulfonate can be used.

[0321] The amount of this component added is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0322] (elastomer)

[0323] The positive photosensitive resin composition may contain an elastomer component in addition to the above.

[0324] The elastomer is used to impart flexibility to the cured product of the positive-type photosensitive resin composition. Conventionally known elastomers can be used as the elastomer, and the polymer constituting the elastomer preferably has a Tg of 20° C. or less.

[0325] Examples of such elastomers include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, and silicone-based elastomers, and these may be used alone or in combination of two or more.

[0326] The amount of the elastomer to be added is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the component (A).

[0327] (Other ingredients)

[0328] In addition to the above, the positive photosensitive resin composition may further contain a dissolution accelerator, a dissolution inhibitor, a coupling agent, a surfactant, a leveling agent, and other components. The positive photosensitive resin composition may further contain inorganic particles such as silica, alumina, and boron nitride; olefin particles such as ethylene particles and propylene particles; and organic particles such as (meth)acrylic particles.

[0329] (Solvent)

[0330] The positive photosensitive resin composition may further contain a solvent in order to dissolve and disperse the above components.

[0331] Specific examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

[0332] The solvent may be used alone or in combination of two or more. The amount of the solvent to be added is not particularly limited, but is preferably adjusted so that the proportion of the solvent in the positive photosensitive resin composition is 20% by mass to 90% by mass.

[0333] The positive photosensitive resin composition can be developed using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH).

[0334] When the composition of the present disclosure is a negative-type photosensitive resin composition, it may contain a photopolymerizable compound having an ethylenically unsaturated group, a thermosetting resin, and a photopolymerization initiator.

[0335] When the composition of the present disclosure is a non-developable thermosetting resin composition, it may contain a curable resin such as an epoxy resin, an amine-based, anhydride-based, or phenol-based curing agent, and, if necessary, a curing accelerator such as imidazole.

[0336] In addition, when the composition of the present disclosure is a photocurable resin composition having no developability, it may contain a photopolymerizable resin having a (meth)acryloyl group or the like and a photopolymerization initiator.

[0337] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

[0338] Description of Reference Numerals

[0339] 10, 30, 40, 50: airtight structure,

[0340] 12: first cover substrate,

[0341] 14: second cover substrate,

[0342] 16, 52: wall components,

[0343] 18: Airtight part,

[0344] 26: basal layer,

[0345] 28: ALD layer.

Claims

1. An airtight structure comprising: Airtight part; a base layer comprising a cured resin covering an edge portion of the airtight portion; and An ALD layer covers the base layer. 2 . The airtight structure according to claim 1 , wherein the glass transition temperature of the cured resin is 150° C. to 400° C. 3 . The airtight structure according to claim 1 , wherein the 5% weight loss temperature of the cured resin is 250° C. to 400° C. The airtight structure according to claim 1 , wherein the storage modulus of the cured resin at 165° C. is 10 MPa to 50 GPa. The airtight structure according to claim 1 , wherein the linear expansion coefficient of the cured resin is 0 ppm / K to 100 ppm / K. The airtight structure according to claim 1 , wherein a difference between a linear expansion coefficient of the cured resin and a linear expansion coefficient of the ALD layer is 0 ppm / K to 30 ppm / K. 7 . The airtight structure according to claim 1 , wherein the airtight portion is formed by a first cover substrate, a second cover substrate, and a wall member that joins the first cover substrate and the second cover substrate and separates an inner side from an outer side of the airtight portion. The airtight structure according to claim 7 , wherein the wall member is made of metal. 9 . The airtight structure according to claim 7 , wherein the wall member is made of resin. 10 . The airtight structure according to claim 1 , wherein the interior of the airtight portion is filled with an inert gas. The airtight structure according to claim 1 , wherein the ALD layer comprises Al 2 O 3 .

12. A method for manufacturing an airtight structure, comprising: forming a curable resin composition layer by covering the edge portion of the airtight portion with the curable resin composition; curing the curable resin composition layer to form a base layer; and forming an ALD layer covering the base layer. 13 . The method for producing an airtight structure according to claim 12 , wherein the curable resin composition has thermosetting properties. 14 . The method for producing an airtight structure according to claim 12 , wherein the curable resin composition is a positive photosensitive resin composition.

15. The method for manufacturing an airtight structure according to claim 12, wherein the airtight portion is formed by joining the top of the first side wall frame and the top of the second side wall frame using a first covering substrate having a first metal side wall frame provided on one surface and a second covering substrate having a second metal side wall frame provided on one surface.

16. An airtight-maintaining base resin composition comprising a curable component. The airtight-keeping base resin composition according to claim 16 , which is a positive-type photosensitive resin composition. The airtight-keeping base resin composition according to claim 16 , which is a negative-type photosensitive resin composition.

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