Protective cover components, component supply sheets, and micro-electromechanical systems

Abstract

The protective cover member provided by the present invention is arranged on a surface of an object, the surface having an opening, wherein the protective cover member is configured from a laminate including a protective film that has such a shape as to cover the opening when the protective cover member is arranged on the surface, and an adhesive layer. When the portion of the protective film that matches the adhesive layer as seen from a direction perpendicular to the main surface of the protective film is defined as a fixed portion of the protective film, an exposed surface of the protective film on the side opposite the side facing the adhesive layer overlaps the fixed portion as seen from the perpendicular direction and has a region A in which the contact angle to with respect methanol is 55 degrees or greater. The protective cover member includes a protective film and an adhesive layer and is suitable for reducing the area of the adhesive layer.

Description

[Technical Field]

[0001] The present invention relates to a protective cover member that is disposed on the surface of an object having an opening, and a micro-electromechanical system comprising a member supply tape for supplying the protective cover member and the protective cover member. [Background technology]

[0002] Protective cover members are known that are placed on the surface of an object having an opening to prevent foreign matter from entering the opening. Patent Document 1 discloses a member comprising a porous membrane mainly composed of polytetrafluoroethylene (hereinafter referred to as PTFE) that allows sound transmission while preventing foreign matter such as water droplets from passing through, and a heat-resistant double-sided adhesive sheet which is an adhesive layer placed in a limited area on at least one main surface of the porous membrane in order to fix the porous membrane to another part. Patent Document 1 attempts to ensure the heat resistance of the member to high temperatures during solder reflow by focusing on the base material of the double-sided adhesive sheet that fixes the member to the surface of the circuit board, which is the object. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2007-81881 [Overview of the project] [Problems that the invention aims to solve]

[0004] In recent years, there has been a demand to place protective cover members over openings in micro-electromechanical systems (MEMS) and other minute products. Furthermore, there is a demand to place protective cover members not only on the outer surface but also on the inner surface of the product, and in order to meet this demand, the area of ​​protective films is being reduced. In this situation, in order to ensure as much air permeability and / or sound permeability as possible through the protective film, it is necessary to reduce the area of ​​the adhesive layer that hinders air and sound permeability, for example, by narrowing the width of the adhesive layer placed at the periphery of the protective film.

[0005] The present invention aims to provide a protective cover member comprising a protective film and an adhesive layer, which is suitable for reducing the area of ​​the adhesive layer. [Means for solving the problem]

[0006] The present invention A protective cover member that is placed on the surface of an object having an opening, The laminate includes a protective film having a shape that covers the opening when the protective cover member is placed on the surface, and an adhesive layer. When the portion of the protective film that coincides with the adhesive layer when viewed from a direction perpendicular to the main surface of the protective film is defined as the fixing portion of the protective film, the exposed surface of the protective film opposite to the side facing the adhesive layer is, Region A, which overlaps with the fixed portion when viewed from the aforementioned vertical direction and has a contact angle with methanol of 55 degrees or more. A protective cover member having, To provide.

[0007] From another perspective, the present invention is The device comprises a base sheet and one or more protective cover members arranged on the base sheet, The protective cover member is a member supply sheet which is the protective cover member of the present invention described above. To provide.

[0008] From another perspective, the present invention is A micro-electromechanical system comprising the protective cover member of the present invention described above, To provide. [Effects of the Invention]

[0009] According to the present invention, a protective cover member comprising a protective film and an adhesive layer is achieved, which is suitable for reducing the area of ​​the adhesive layer. [Brief explanation of the drawing]

[0010] [Figure 1A] Figure 1A is a schematic cross-sectional view showing an example of a protective cover member of the present invention. [Figure 1B] Figure 1B is a plan view of the protective cover member 1 shown in Figure 1A, viewed from the side of the protective film 2. [Figure 1C] Figure 1C is a plan view of the protective cover member 1 shown in Figure 1A, viewed from the side of the adhesive layer 3. [Figure 2A] Figure 2A is a schematic diagram illustrating fluid spillage when the exposed surface of the protective film does not include region A. [Figure 2B] Figure 2B is a schematic diagram showing an example of a state that a fluid can take when the exposed surface of the protective film has region A. [Figure 3] Figure 3 is a schematic cross-sectional view showing an example of a protective cover member of the present invention. [Figure 4] Figure 4 is a schematic cross-sectional view showing an example of how the protective cover member of the present invention is arranged on an object. [Figure 5] Figure 5 is a schematic cross-sectional view showing an example of how the protective cover member of the present invention is arranged on an object. [Figure 6] Figure 6 is a schematic cross-sectional view showing an example of a protective cover member of the present invention. [Figure 7] Figure 7 is a schematic cross-sectional view showing an example of a protective cover member of the present invention. [Figure 8] Figure 8 is a schematic plan view showing an example of a sheet for supplying components according to the present invention. [Modes for carrying out the invention]

[0011] A protective cover member according to a first aspect of the present invention is A protective cover member that is placed on the surface of an object having an opening, The laminate includes a protective film having a shape that covers the opening when the protective cover member is placed on the surface, and an adhesive layer. When the portion of the protective film that coincides with the adhesive layer when viewed from a direction perpendicular to the main surface of the protective film is defined as the fixing portion of the protective film, the exposed surface of the protective film opposite to the side facing the adhesive layer is, Region A, which overlaps with the fixed portion when viewed from the aforementioned vertical direction and has a contact angle with methanol of 55 degrees or more. It holds.

[0012] In a second embodiment of the present invention, for example, in the protective cover member according to the first embodiment, the contact angle with methanol is 55 degrees or more over the entire exposed surface on the opposite side of the fixing portion.

[0013] In a third aspect of the present invention, for example, in the protective cover member according to the first or second aspect, the fixing portion is located on the peripheral edge of the protective film when viewed from the vertical direction.

[0014] In a fourth aspect of the present invention, for example, in a protective cover member according to any one of the first to third aspects, the adhesive layer is in contact with the protective film.

[0015] In a fifth embodiment of the present invention, for example, in a protective cover member according to any one of the first to fourth embodiments, the adhesive layer is located on the side of the protective cover member that faces the surface of the object, relative to the protective film.

[0016] In a sixth embodiment of the present invention, for example, in a protective cover member according to any one of the first to fifth embodiments, the adhesive layer includes a layer formed from a thermosetting adhesive composition.

[0017] In a seventh aspect of the present invention, for example, in the protective cover member according to the sixth aspect, the storage modulus of the thermosetting adhesive composition is 1.0 × 10 at 130 to 170°C. 3 It is Pa or higher.

[0018] In the eighth aspect of the present invention, for example, in the protective cover member according to the sixth or seventh aspect, the storage modulus of the thermosetting adhesive composition after heat curing is 1.0 × 10 at 130 to 170°C. 8 It is below Pa.

[0019] In the ninth aspect of the present invention, for example, in a protective cover member according to any one of the first to eighth aspects, the adhesive layer is arranged on the periphery of the protective film when viewed from a direction perpendicular to the main surface of the protective film, and the ratio L2 / L1 of the length of the portion of the shortest line segment from the center of the protective film to the outer circumference of the protective film that overlaps with the adhesive layer to the shortest line segment L1 is 0.5 or less.

[0020] In a tenth embodiment of the present invention, for example, in a protective cover member according to any one of the first to ninth embodiments, the protective film has breathability in the thickness direction.

[0021] In an eleventh aspect of the present invention, for example, in a protective cover member according to any one of the first to tenth aspects, the protective film includes a porous film or a microporous film, and the average pore diameter of the porous film and the microporous film is 0.01 μm or more and less than 3 μm.

[0022] In a twelfth aspect of the present invention, for example, in a protective cover member according to any one of the first to eleventh aspects, the protective film includes a polytetrafluoroethylene film.

[0023] In a thirteenth aspect of the present invention, for example, in a protective cover member according to any one of the first to twelfth aspects, the area of ​​the protective film is 175 mm². 2 The following applies:

[0024] In a fourteenth aspect of the present invention, for example, in a protective cover member according to any one of the first to thirteenth aspects, the laminate further includes a base film located on the side of the adhesive layer relative to the protective film.

[0025] In a 15th aspect of the present invention, for example, a protective cover member according to any one of the first to 14th aspects is for use in a micro-electromechanical system (MEMS).

[0026] In the sixteenth embodiment of the present invention, for example, the protective cover member according to the fifteenth embodiment is used by being placed inside the MEMS.

[0027] A sheet for supplying components according to the 17th aspect of the present invention is: The device comprises a base sheet and one or more protective cover members arranged on the base sheet, The protective cover member is a protective cover member according to any one of the first to sixteenth embodiments.

[0028] A micro-electromechanical system according to the 18th aspect of the present invention is: It comprises a protective cover member according to any one of the 1st to 16th embodiments.

[0029] Embodiments of the present invention will be described below with reference to the drawings. The present invention is not limited to the following embodiments.

[0030] [Protective cover component] An example of the protective cover member of this embodiment is shown in Figures 1A, 1B, and 1C. Figure 1B is a plan view of the protective cover member 1 of Figure 1A as seen from the side of the protective film 2. Figure 1C is a plan view of the protective cover member 1 of Figure 1A as seen from the side of the adhesive layer 3. Figure 1A shows the cross section 1A-1A of Figures 1B and 1C. In Figures 1B and 1C, the protective cover member 1 is viewed from a direction perpendicular to the main surface of the protective film 2. The protective cover member 1 is a member that is placed on the surface (placement surface) of an object having a surface with an opening. By placing the protective cover member 1 on the placement surface, for example, it is possible to prevent foreign matter from entering and / or from the opening, in other words, from entering through the opening. The protective cover member 1 is composed of a laminate 4 including a protective film 2 and an adhesive layer 3. The protective film 2 has a shape that covers the opening when the protective cover member 1 is placed on the placement surface. The adhesive layer 3 is bonded to the protective film 2. The protective cover member 1 can be fixed to the surface on which the object is placed by the adhesive layer 3.

[0031] When viewed from a direction perpendicular to the main surface of the protective film 2, the portion of the protective film 2 that coincides with the adhesive layer 3 can be defined as the fixing portion 21 of the protective film 2. The exposed surface 22 of the protective film 2 opposite to the side facing the adhesive layer 3 overlaps with the fixing portion 21 when viewed from a direction perpendicular to the main surface of the protective film 2, and has a contact angle θ with respect to methanol. M It has a region A where the temperature is 55 degrees or higher.

[0032] When the area of the adhesive layer 3 is reduced, it becomes difficult to join the protective film 2 and the adhesive layer 3 and maintain the joining. In order to make the joining of the two more reliable, it is conceivable to use a heat-pressurization treatment such as hot pressing. However, according to studies conducted by the present inventors, particularly when the two are joined using a heat-pressurization treatment, it has been found that when another member is combined not on the adhesive layer 3 side of the protective film 2 but on the side opposite to the adhesive layer 3 side, the air permeability and sound permeability of the protective cover member 1 tend to be impaired. According to further studies, the above tendency is typically caused by the fact that a fluid 5 such as an adhesive for joining another member to the protective cover member 1 or a surface treatment liquid applied to the protective film 2 before disposing another member spreads from the fixing portion 21 of the protective film 2 to the air-permeable / sound-permeable region 23 and blocks the region 23 (see FIG. 2A). In the protective cover member 1 of the present embodiment, since the exposed surface 22 has the region A, the protrusion of the fluid 5 from the fixing portion 21 to the air-permeable / sound-permeable region 23 can be suppressed (see FIG. 2B). It should be noted that the surface tension (at 20°C) of an organic solvent usually contained in an adhesive or the like is generally in the range of about 20 to 40 mN / m. In consideration of this, the contact angle θ with respect to methanol having a surface tension (22.5 mN / m; 20°C) close to the lower limit of the above range M is defined.

[0033] The contact angle θ of the region A M may be 58 degrees or more, 60 degrees or more, 63 degrees or more, 65 degrees or more, 68 degrees or more, 70 degrees or more, 73 degrees or more, and further may be 75 degrees or more. The upper limit of the contact angle θ of the region A M is, for example, 130 degrees or less, and may be 120 degrees or less, 110 degrees or less, 100 degrees or less, 90 degrees or less, 85 degrees or less, 80 degrees or less, 75 degrees or less, and further may be less than 73 degrees. The contact angle θ M can be evaluated in accordance with the sessile drop method specified in Japanese Industrial Standards (hereinafter referred to as JIS) R3257 (provided that a methanol drop with a volume of 2 μL is used instead of a water drop). The evaluation temperature is 25°C.

[0034] The contact angle θ of the region A MThis can vary depending on, for example, the material and properties of the protective film 2 (thickness, average pore diameter, porosity, condition of the exposed surface 22, surface free energy, surface roughness, etc.), whether or not various treatments are applied to the protective film 2, the properties of the adhesive layer 3 (thickness, storage modulus, surface free energy, etc.), the composition and properties of the adhesive composition used to form the adhesive layer 3 (storage modulus, surface free energy, etc.), and the bonding conditions between the protective film 2 and the adhesive layer 3.

[0035] The shape of region A is not limited as long as it overlaps with the fixing portion 21 when viewed from a direction perpendicular to the main surface of the protective film 2. The contact angle θ of the portion of region A that overlaps with the fixing portion 21 is also considered. M If the angle θ1 (for example, 55 degrees) is greater than or equal to a certain angle θ, then the contact angle θ of region A M Assume that θ is greater than or equal to θ1.

[0036] In the protective cover member 1 shown in Figures 1A to 1C, the entire exposed surface 22 on the opposite side of the fixing portion 21, in other words, the entire portion of the exposed surface 22 that coincides with the fixing portion 21 when viewed from a direction perpendicular to the main surface of the protective film 2, has a contact angle θ M The temperature is 55 degrees or higher.

[0037] The fixing portion 21 in Figures 1A to 1C is located on the periphery of the protective film 2 when viewed from a direction perpendicular to the main surface of the protective film 2. Furthermore, the shape of the fixing portion 21 in Figures 1A to 1C is frame-like when viewed from the aforementioned perpendicular direction. However, the shape of the fixing portion 21 and its position on the protective film 2 are not limited to the above examples. In addition, the region 23 surrounded by the fixing portion 21 on the protective film 2 when viewed from the aforementioned perpendicular direction can become a ventilated / sound-permeable region in the protective cover member 1 through which gas and / or sound can mainly pass.

[0038] The area of ​​region 23 is, for example, 20 mm². 2 The following is 15mm 2 Below, 12.5mm 2 Below, 10mm 2 Below, 7.5mm 2 Below, 5mm 2 Below, 2.5mm 2 Below, 2mm 2 Below, and furthermore, 1.5mm2 The following is also possible. Protective cover member 1 whose area of ​​region 23 is within the above range is suitable for placement on circuit boards and MEMS that typically have small-diameter openings, for example. The lower limit of the area of ​​region 23 is, for example, 0.008 mm 2 That concludes the explanation. However, the area of ​​region 23 may be larger depending on the type of object on which the protective cover member 1 is placed.

[0039] Region A and region 23 may overlap when viewed from a direction perpendicular to the main surface of the protective film 2.

[0040] The adhesive layer 3 in Figures 1A to 1C is in contact with the protective film 2. More specifically, the adhesive layer 3 is bonded to the protective film 2. However, other layers may be placed between the adhesive layer 3 and the protective film 2. A heat press or other heat and pressure treatment may be used to bond the adhesive layer 3 and the protective film 2.

[0041] The components contained in the adhesive layer 3 (hereinafter referred to as the components of the adhesive layer 3) may or may not penetrate into the interior of the protective film 2. If the components of the adhesive layer 3 penetrate into the interior of the protective film 2, the penetration does not need to reach the exposed surface 22 of the protective film 2. Including the embodiment in which the penetration does not penetrate into the interior of the protective film 2, the fact that the penetration does not reach the exposed surface 22 can contribute to the exposed surface 22 having region A. According to the inventors' studies, penetration of the components of the adhesive layer 3 is likely to occur when the adhesive layer 3 and the protective film 2 are joined, in particular when the adhesive layer 3 is a layer formed from a thermosetting adhesive composition or when the adhesive layer 3 and the protective film 2 are joined using a heat-pressure treatment.

[0042] The degree to which the components of the adhesive layer 3 penetrate into the interior of the protective film 2 can be expressed, for example, by the maximum penetration depth of the above components into the protective film 2. The maximum penetration depth may be less than the thickness of the protective film 2, and may be 95% or less, 90% or less, 70% or less, 50% or less, 30% or less, or even 10% or less of the thickness of the protective film 2.

[0043] The adhesive layer 3 in Figures 1A to 1C is positioned in a portion of the protective film 2 when viewed from a direction perpendicular to the main surface of the protective film 2. The shape of the adhesive layer 3, when viewed from the aforementioned perpendicular direction, is the shape of the peripheral edge of the protective film 2, more specifically, frame-like. In the area 23 of the protective film 2 where the adhesive layer 3 is not positioned, better ventilation and / or sound transmission is possible compared to the area where the adhesive layer 3 is positioned. However, the shape of the adhesive layer 3 is not limited to the above example. For example, if the shape of the protective film 2 when viewed from a direction perpendicular to the main surface is circular, the shape of the adhesive layer 3 may be ring-shaped when viewed from the aforementioned perpendicular direction.

[0044] The thickness of the adhesive layer 3 is, for example, 3 to 200 μm, and may be 5 to 100 μm, 10 to 50 μm, or even 20 to 40 μm.

[0045] The total area of ​​the adhesive layer 3 is, for example, 0.1 to 10 mm². 2 And, 0.5~5mm 2 , 0.8~4mm 2 Furthermore, 1-3mm 2 It is also possible that the width of the frame-shaped adhesive layer 3 (corresponding to the width of the fixing part 21) is, for example, 50 to 3000 μm, and may be 100 to 1000 μm, 150 to 800 μm, or even 200 to 500 μm.

[0046] The adhesive layer 3 in Figures 1A to 1C is positioned at the periphery of the protective film 2 when viewed from a direction perpendicular to the main surface of the protective film 2. At this time, when viewed from the above perpendicular direction, the shortest line segment S from the center O of the protective film 2 to the outer circumference of the protective film 2 is min The line segment S with respect to length L1 min The ratio L2 / L1 of the length L2 of the portion overlapping with the adhesive layer 3 may be 0.5 or less, 0.3 or less, 0.2 or less, or even 0.1 or less. The lower limit of the ratio L2 / L1 is, for example, 0.05 or more. The center O of the protective film 2 can be determined as the centroid of the shape of the protective film 2 when viewed from a direction perpendicular to the main surface of the protective film 2.

[0047] The adhesive layer 3 includes a layer (hereinafter referred to as layer B) formed from an adhesive composition. The adhesive layer 3 may have a single-layer structure consisting of layer B, or it may have a laminated structure including layer B. The laminated structure may have two or more layers B.

[0048] The adhesive layer 3 may include a base material and a layer B disposed on at least one surface of the base material. An example of this embodiment is shown in Figure 3. The adhesive layer 3 in Figure 3 has a base material 32 and layers B31 provided on both surfaces of the base material 32. One layer B31 is in contact with the protective film 2. The other layer B31 constitutes the bonding surface 11 of the protective cover member 1 to the surface on which the object is placed. The configuration of each layer B31 may be the same or different from each other.

[0049] Examples of the base material 32 include films, nonwovens, and foams made of resins, metals, or composites thereof. Examples of resins include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate (PET), silicone resins, polycarbonates, polyimides, polyamide-imides, polyphenylene sulfide, polyether ether ketone (PEEK), and fluororesins. Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (ETFE). Examples of metals include stainless steel and aluminum. However, the resins and metals are not limited to the examples above.

[0050] The base material 32 may contain a heat-resistant material. A protective cover member 1 equipped with a base material 32 containing a heat-resistant material is suitable for use at high temperatures, depending on the materials of the other layers constituting the protective cover member 1. Examples of heat-resistant materials are metals and heat-resistant resins. Heat-resistant resins typically have a melting point of 150°C or higher. The melting point of a heat-resistant resin may be 160°C or higher, 200°C or higher, 220°C or higher, 240°C or higher, 250°C or higher, 260°C or higher, or even 300°C or higher. Examples of heat-resistant resins are silicone resins, polyimides, polyamide-imides, polyphenylene sulfide, PEEK, and fluororesins. The fluororesin may be PTFE. PTFE has particularly excellent heat resistance.

[0051] Examples of adhesive compositions that can form layer B31 include thermosetting adhesive compositions, pressure-sensitive adhesive compositions, and ultraviolet (UV) curable adhesive compositions. Layer B31 may be formed from a thermosetting adhesive composition; in other words, the adhesive layer 3 may include a layer formed from a thermosetting adhesive composition (hereinafter referred to as the thermosetting adhesive layer). The adhesive layer 3 including the thermosetting adhesive layer is more suitable for bonding with the protective film 2 by heat and pressure treatment. The thermosetting adhesive layer is formed, for example, by coating and drying the thermosetting adhesive composition C.

[0052] The storage modulus G' of adhesive composition C is 1.0 × 10⁻⁶ at 130-170°C. 3 It may be Pa or higher. 130-170°C corresponds to the typical curing temperature of thermosetting resin compositions and the typical temperature of heat-pressure treatment. The storage modulus G' of adhesive composition C is 3.0 × 10 at 130-170°C. 3 Pa or higher, 5.0×10 3 Pa or higher, 7.0×10 3 Pa or more, 1.0×10 4 Pa or more, 4.6×10 4 Pa or higher, 5.0×10 4 Pa or higher, 6.0×10 4 Pa or higher, 7.0×10 4 Pa or more, 1.0×10 5 Pa or higher, 3.0×10 5 Pa or higher, 5.0×10 5Pa or higher, 7.0×10 5 Pa or higher, and even 9.0 x 10 5 The storage modulus G in the same temperature range may be greater than or equal to Pa. ’ The upper limit is, for example, 5.0 × 10 6 The storage modulus G of adhesive composition C at 130-170°C is less than or equal to Pa. The adhesive layer 3, which includes a layer formed from the adhesive composition C, exhibits excellent shape retention when heated, making it more suitable for bonding with the protective film 2 by heat and pressure treatment. ’ Being within the above range can help suppress the penetration of components of the adhesive layer 3 into the interior of the protective film 2.

[0053] The storage modulus G' of adhesive composition C after heat curing is 1.0 × 10⁻⁶ at 130-170°C. 8 The hardness may be less than or equal to Pa. The adhesive layer 3, which includes a layer formed from the adhesive composition C, is not too hard and has excellent bonding properties. The storage modulus G' after heat curing is 5.0 × 10 at 130 to 170°C. 7 Pa or less, 3.0×10 7 Pa or less, 1.8×10 7 Pa or less, 1.7×10 7 Pa or less, 1.0×10 7 Pa or less, 5.0×10 6 Pa or less, 2.0×10 6 Pa or less, 1.0×10 6 Pa or less, and even 9.6 × 10 5 It may be less than or equal to Pa. The lower limit of the storage modulus G' after thermosetting in the same temperature range is, for example, 5.0 × 10⁻⁶. 4 It is Pa or higher.

[0054] The storage modulus G' of adhesive composition C after heat curing is 1.0 × 10 at 250°C. 5 The pressure may be Pa or higher. The adhesive layer 3, which includes a layer formed from the adhesive composition C, exhibits excellent durability in high-temperature treatments such as solder reflow, even when its area is reduced. The storage modulus G' after heat curing is 3.0 × 10 at 250°C. 5 Pa or higher, 5.0×10 5 Pa or higher, 7.0×10 5Pa or more, 1.0×10 6 Pa or more, 1.1×10 6 Pa or higher, 5.0×10 6 Pa or more, 1.0×10 7 Pa or higher, 2.0×10 7 Pa or higher, and even 2.2 × 10⁻⁶ 7 The storage modulus G after thermosetting in the same temperature range may be greater than Pa. ’ The upper limit is, for example, 5.0 × 10 8 It is less than or equal to Pa, and 1.0 × 10 8 Below Pa, and even 5.0 × 10 7 Please refer to the following below Pa.

[0055] The storage modulus G' of adhesive composition C can be evaluated by using a film of adhesive composition C or a heat-cured film (22.5 mm in length and 10 mm in width) as a test specimen and heating it at a heating rate of 10°C / min using a forced vibration type solid viscoelasticity measuring device. However, the measurement direction (vibration direction) of the test specimen is the length direction, and the vibration frequency is 1 Hz.

[0056] Examples of adhesive compositions C that can satisfy each of the above storage moduli G' are described below. However, adhesive compositions C are not limited to the following examples.

[0057] Adhesive composition C is, for example, an acrylic composition containing an acrylic polymer. Acrylic compositions typically contain an acrylic polymer (hereinafter referred to as acrylic polymer D) as the base polymer of the adhesive composition. The content of acrylic polymer D in the acrylic composition is, for example, 35% by weight or more, and may be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, and even 90% by weight or more. The upper limit of the content of acrylic polymer D is, for example, 100% by weight or less, and may be 95% by weight or less, and even 90% by weight or less.

[0058] The weight-average molecular weight of acrylic polymer D is preferably 200,000 or more, but may be 400,000 or more, 600,000 or more, 800,000 or more, or even 1,000,000 or more. The upper limit of the weight-average molecular weight of acrylic polymer D is, for example, 5,000,000 or less. The adhesive composition C may contain acrylic polymer D with a weight-average molecular weight of 200,000 or more at a content of 35% by weight or more.

[0059] Adhesive composition C is thermosetting and contains a thermosetting group. Examples of thermosetting groups include at least one selected from epoxy groups, hydroxyphenyl groups, carboxyl groups, hydroxyl groups, carbonyl groups, azilidinyl groups, and amino groups. The thermosetting group may be at least one selected from epoxy groups, hydroxyphenyl groups, and carboxyl groups, or it may be an epoxy group and / or a hydroxyphenyl group. Note that the epoxy group includes a glycidyl group.

[0060] In adhesive composition C, the acrylic polymer D may have thermosetting groups. In this case, compared to the case where the thermosetting resin described later has thermosetting groups, the crosslinked structure after thermosetting becomes more homogeneous, and the heat resistance of the cured adhesive layer after thermosetting can be improved. Examples of thermosetting groups that the acrylic polymer D may have are at least one selected from epoxy groups, carboxyl groups, hydroxyl groups, carbonyl groups, azilidinyl groups, and amino groups. The thermosetting group that the acrylic polymer D may have may be an epoxy group and / or a carboxyl group, or it may be an epoxy group.

[0061] The glass transition temperature (Tg) of acrylic polymer D is, for example, -15 to 40°C, but may also be -10 to 30°C, or even -5 to 20°C.

[0062] The adhesive composition C may further contain a thermosetting resin, in which case the content of the thermosetting resin in the adhesive composition C is preferably smaller than the content of the acrylic polymer D in the adhesive composition C. The higher the content of the acrylic polymer D, the higher the storage modulus G' of the adhesive composition C at 130-170°C may be. The thermosetting resin may have thermosetting groups, and a thermosetting resin having thermosetting groups can function as a crosslinking agent. Examples of thermosetting groups are as described above.

[0063] The content of the thermosetting resin in adhesive composition C may be, for example, 50% by weight or less, but may also be 40% by weight or less, 35% by weight or less, 30% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less. The lower limit of the thermosetting resin content may be, for example, 0% by weight or more, but may also be 5% by weight or more. Adhesive composition C may not contain any thermosetting resin.

[0064] Examples of thermosetting resins include phenolic resins, epoxy resins, urea resins, melamine resins, and unsaturated polyester resins. However, thermosetting resins are not limited to the above examples. When the thermosetting resin is a phenolic resin and / or epoxy resin, and especially when it is a phenolic resin, the heat resistance of the cured adhesive layer after thermosetting may be improved.

[0065] Examples of phenolic resins include novolac-type phenolic resins such as phenol novolac resins, phenol biphenyl resins, phenol aralkyl resins, cresol novolac resins, tert-butylphenol novolac resins, and nonylphenol novolac resins, as well as resol-type phenolic resins. However, phenolic resins are not limited to the above examples.

[0066] The hydroxyl value of the phenolic resin is, for example, 100 to 500 g / eq, and may also be 100 to 400 g / eq.

[0067] The weight-average molecular weight of the thermosetting resin is, for example, 100 to 3000, and may also be 150 to 2000.

[0068] Thermosetting resins can be formed by known manufacturing methods.

[0069] Examples of the composition of acrylic polymer D are described below. However, acrylic polymer D is not limited to having the following compositions.

[0070] Acrylic polymer D may have a constituent unit E derived from at least one monomer selected from the following monomers: alkyl acrylates having C1-C8 alkyl groups such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate and hexyl acrylate; alkyl methacrylates having C1-C8 alkyl groups such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate; acrylonitrile; styrene; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid-free monomers such as maleic anhydride and itaconic anhydride. Water monomers; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate; sulfonic acid group-containing monomers such as styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloyloxynaphthalenesulfonic acid; and phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate. A preferred example of constituent unit E is a unit derived from at least one monomer selected from alkyl acrylates having C1-C4 alkyl groups, alkyl methacrylates having C1-C4 alkyl groups, and acrylonitrile. A more preferred example is a unit derived from at least one monomer selected from ethyl acrylate, butyl acrylate, and acrylonitrile. It is preferable that the acrylic polymer D has all of the constituent units derived from ethyl acrylate, butyl acrylate, and acrylonitrile. Constituent unit E does not have a thermosetting group.

[0071] The content of constituent unit E in acrylic polymer D is, for example, 70% by weight or more, and may be 80% by weight or more, or even 90% by weight or more. Acrylic polymer D may be composed of constituent unit E.

[0072] If the acrylic polymer D contains units derived from acrylonitrile (acrylonitrile units), the content of such units in the acrylic polymer D may be, for example, 5% by weight or more, 10% by weight or more, 15% by weight or more, or even 20% by weight or more. The upper limit of the content of such units is, for example, 40% by weight or less.

[0073] Acrylic polymer D may have a constituent unit F having a thermosetting group. Examples of constituent unit F are units derived from alkyl acrylates and alkyl methacrylates to which thermosetting groups have been introduced. Specific examples of thermosetting groups, alkyl acrylates, and alkyl methacrylates are as described above. More specific examples of constituent unit F are glycidyl methyl acrylate, glycidyl ethyl acrylate, glycidyl 2-ethylhexyl acrylate, carboxymethyl acrylate, and azilidinyl methyl acrylate. Acrylic polymer D does not have to have constituent unit F, but in this case, the adhesive composition C usually contains a thermosetting resin having a thermosetting group.

[0074] If the acrylic polymer D has constituent units F, the content of constituent units F in the acrylic polymer D may be, for example, 30 to 95% by weight, or 40 to 90% by weight. In this case, the content of constituent units E does not have to be within the range exemplified above, and the sum of the content of constituent units E and constituent units F may be, for example, 70% by weight or more, 80% by weight or more, or even 90% by weight or more. The acrylic polymer D may be composed of constituent units E and constituent units F.

[0075] When the acrylic polymer D has constituent units F having epoxy groups, the epoxy value of the acrylic polymer D is, for example, 0.15 to 0.65 eq / kg, and may also be 0.20 to 0.50 eq / kg.

[0076] Acrylic polymer D can be formed by known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.

[0077] Adhesive composition C may contain a filler. Examples of fillers include inorganic fillers and organic fillers. From the viewpoint of improving handling properties, adjusting melt viscosity, and imparting thixotropic properties, inorganic fillers are preferred for adhesive composition C.

[0078] Examples of inorganic fillers include silica, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, antimony trioxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate, and boron nitride. Silica may be crystalline or amorphous. Examples of organic fillers include polyimide, polyamide-imide, polyetheretherketone, polyetherimide, polyesterimide, nylon, and silicone.

[0079] The average particle size of the filler is, for example, 0.005 to 10 μm, but may also be 0.05 to 1 μm. Fillers with mutually different average particle sizes may be combined. The average particle size of the filler can be determined using a photometric particle size analyzer (for example, HORIBA, model name: LA-910).

[0080] Examples of filler shapes include spherical and ellipsoidal shapes.

[0081] Adhesive composition C may contain other components besides those described above. Examples of other components include additives such as flame retardants, silane coupling agents, ion trapping agents, and thermosetting accelerators.

[0082] Examples of flame retardants include antimony trioxide, antimony pentoxide, and brominated epoxy resins. Examples of silane coupling agents include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Examples of ion trapping agents include hydrotalcites and bismuth hydroxide. Examples of thermosetting accelerator catalysts are salts having a triphenylphosphine skeleton, an amine skeleton, a triphenylborane skeleton, or a trihalogen-borane skeleton.

[0083] Examples of pressure-sensitive adhesive compositions that can form layer B31 include acrylic, silicone, urethane, and rubber-based adhesive compositions.

[0084] The protective film 2 may be non-permeable in the thickness direction or permeable in the thickness direction. If the protective film 2 is permeable in the thickness direction, the arrangement of the protective cover member 1 can ensure airflow through the opening of the object while preventing the intrusion of foreign matter through the opening. Ensuring airflow makes it possible, for example, to adjust the pressure through the opening of the object or mitigate pressure fluctuations. An example of mitigating pressure fluctuations is shown below. A semiconductor element may be placed so as to cover one of the openings of a through-hole provided in a circuit board, and then subjected to a heat treatment such as solder reflow. Here, by placing the protective cover member 1 so as to cover the other opening, the intrusion of foreign matter into the element through the through-hole during the heat treatment can be suppressed. If the protective film 2 is permeable in the thickness direction, the pressure rise in the through-hole due to heating can be mitigated, and damage to the element due to the pressure rise can be prevented. Examples of semiconductor elements are MEMS such as microphones, pressure sensors, and acceleration sensors. These elements have permeable and / or sound-permeable openings, and can be placed on a circuit board so that the openings face the through-holes. The protective cover member 1 may be placed on the semiconductor element after manufacturing so as to cover the opening of the element. It may also be placed inside the element. If the protective film 2 has permeability in the thickness direction, the placed protective cover member 1 can function, for example, as a ventilation member that prevents foreign matter from entering through the opening of the object while ensuring ventilation through the opening, and / or as a sound-conducting member that prevents foreign matter from entering through the opening of the object while ensuring sound transmission through the opening. Even if the protective film 2 is not permeable in the thickness direction, the placed protective cover member 1 can still function as a sound-conducting member because sound can be transmitted by vibration of the protective film 2.

[0085] The air permeability of the protective film 2, which has air permeability in the thickness direction, is expressed by the air permeability (Gurley air permeability) determined in accordance with the air permeability measurement method B (Gurley method) specified in JIS L1096, and is, for example, 0.1 seconds / 100 mL or more and 10,000 seconds / 100 mL or less. The lower limit of the Gurley air permeability may be 0.15 seconds / 100 mL or more, 0.3 seconds / 100 mL or more, 0.5 seconds / 100 mL or more, and even 0.6 seconds / 100 mL or more. The upper limit of the Gurley air permeability may be 5,000 seconds / 100 mL or less, 1,000 seconds / 100 mL or less, 300 seconds / 100 mL or less, 200 seconds / 100 mL or less, and even less than 100 seconds / 100 mL. Note that a protective film 2 with an air permeability of more than 10,000 seconds / 100 mL can be judged to be a non-air permeable film in the thickness direction.

[0086] The protective film 2 may be waterproof. A protective cover member 1 equipped with a waterproof protective film 2 can function, for example, as a waterproof and breathable member and / or a waterproof and soundproof member after being placed on an object. The water pressure resistance of the waterproof protective film 2 is, for example, 5 kPa or more, as determined in accordance with the water resistance test method A (low water pressure method) or method B (high water pressure method) specified in JIS L1092.

[0087] Examples of materials that make up protective film 2 include metals, resins, and composite materials thereof.

[0088] Examples of resins and metals that can constitute the protective film 2 are the same as examples of resins and metals that can constitute the substrate 32 of the adhesive layer 3. However, the resins and metals are not limited to the above examples.

[0089] The protective film 2 may be made of a heat-resistant material. Examples of heat-resistant materials are as described above in the description of the base material 32.

[0090] The protective film 2 may also include a PTFE film.

[0091] The protective film 2 may include a porous film or a microporous film. The protective film 2, which has permeability in the thickness direction, may include a porous film or a microporous film. A film with a permeability in the thickness direction expressed by the Gurley number of 20 seconds / 100 mL or less can be determined as a porous film, while a film with a permeability exceeding 20 seconds / 100 mL but not exceeding 10,000 seconds / 100 mL can be determined as a microporous film.

[0092] The average pore size of porous and microporous membranes may be 0.01 μm or more and less than 3 μm. The lower limit of the average pore size may be 0.01 μm or more, 0.05 μm or more, and even 0.1 μm or more. The upper limit of the average pore size may be 3 μm or less, less than 3 μm, 2.5 μm or less, 2 μm or less, 1.5 μm or less, and even 1 μm or less. Protective membrane 2 including a porous or microporous membrane having an average pore size of less than 3 μm is particularly suitable for suppressing the penetration of components of the adhesive layer 3 when bonding with the adhesive layer 3, especially when bonding using heat and pressure treatment. Protective membrane 2 including a porous or microporous membrane having an average pore size of 0.01 μm or more is suitable for suppressing the overflow of components of the adhesive layer 3 into region 23 and deformation of the adhesive layer 3 when bonding with the adhesive layer 3, especially when bonding using heat and pressure treatment. The average pore size of the protective membrane can be evaluated in accordance with ASTM F316-86.

[0093] The porous membrane may be a stretched porous membrane. The stretched porous membrane may be a stretched porous membrane of fluororesin, particularly a PTFE stretched porous membrane. A PTFE stretched porous membrane is usually formed by stretching a paste extruded or cast membrane containing PTFE particles. A PTFE stretched porous membrane is composed of fine fibrils of PTFE and may have nodes in which the PTFE is aggregated compared to the fibrils. A PTFE stretched porous membrane makes it possible to achieve a high level of both foreign matter prevention and permeability. A known stretched porous membrane can be used for the protective membrane 2.

[0094] The protective film 2, which has breathability in the thickness direction, may include a perforated film having a plurality of through holes connecting the two main surfaces. The perforated film may be a film in which a plurality of through holes are provided in a base film having a non-porous substrate structure, such as a non-porous film. The perforated film may not have ventilation paths in the thickness direction other than the plurality of through holes. The through holes may extend in the thickness direction of the perforated film, or they may be straight holes extending linearly in the thickness direction. The shape of the opening of the through holes may be a circle or an ellipse when viewed perpendicular to the main surface of the perforated film. The perforated film can be formed, for example, by laser processing of the base film, or by ion beam irradiation followed by chemical etching.

[0095] The protective film 2, which has breathability in the thickness direction, may include nonwoven fabric, woven fabric, mesh, or net.

[0096] The protective film 2 is not limited to the above example.

[0097] The protective film 2 in Figures 1A to 1C is rectangular when viewed from a direction perpendicular to its main surface. However, the shape of the protective film 2 is not limited to the above example; for example, when viewed from the above perpendicular direction, it may be a polygon including a square and a rectangle, a circle, or an ellipse. The polygon may be a regular polygon. The corners of the polygon may be rounded.

[0098] The thickness of protective film 2 is, for example, 1 to 100 μm.

[0099] The area of ​​protective film 2 is, for example, 175 mm². 2 The following is 150mm 2 Below, 125mm 2 Below, 100mm 2 Below, 75mm 2 Below, 50mm 2 Below, 25mm 2 Below, 20mm 2 Below, 15mm 2 Below, 10mm 2 Below, 7.5mm 2 Below, 5mm 2 Below, and even 2.5mm 2may be less than or equal to the foregoing. The protective cover member 1 in which the area of the protective film 2 falls within the above range is suitable for arrangement on, for example, a circuit board or MEMS that usually has a small-diameter opening. The lower limit of the area of the protective film 2 is, for example, 0.20 mm 2 or more. However, the area of the protective film 2 may be larger than the above range depending on the type of the object on which the protective cover member 1 is arranged.

[0100] The basis weight (weight per unit area) of the protective film 2 is, for example, 1 to 30 g / m 2 . The lower limit of the basis weight is 0.5 g / m 2 or more, 0.8 g / m 2 or more, 1.0 g / m 2 or more, 1.2 g / m 2 or more, 1.4 g / m 2 or more, 1.5 g / m 2 or more, 1.7 g / m 2 or more, 2.0 g / m 2 or more, 2.5 g / m 2 or more, and may even exceed 3.0 g / m 2 . The upper limit of the basis weight is 25 g / m 2 or less, 22 g / m 2 or less, 20 g / m 2 or less, 18 g / m 2 or less, 15 g / m 2 or less, 13 g / m 2 or less, 10 g / m 2 or less, 8 g / m 2 or less, 6 g / m 2 or less, 5 g / m 2 or less, 4 g / m 2 or less, 3 g / m 2 or less, 2.5 g / m 2 or less, 2 g / m 2 or less, and may even be 1.8 g / m 2 or less.

[0101] The protective film 2 may be subjected to various treatments such as water repellent treatment, liquid repellent treatment, and coloring treatment. Various treatments can be carried out based on known methods.

[0102] As the protective film 2, the contact angle θ with respect to methanol MA film with a contact angle of 75 degrees or higher may be used. In other words, the inherent contact angle θ of the protective film 2. M The angle may be 75 degrees or more. The inherent contact angle θ of the protective film 2 M The contact angle θ may be 77 degrees or more, 80 degrees or more, 82 degrees or more, 85 degrees or more, 87 degrees or more, 89 degrees or more, or even 90 degrees or more. M The protective film 2 having is particularly suitable for suppressing the penetration of components of the adhesive layer 3 when bonding with the adhesive layer 3, especially when bonding using heat and pressure treatment. The protective film 2 has an inherent contact angle θ M This varies depending, for example, on the material and properties of the protective film 2 (thickness, average pore size, porosity, surface free energy, surface roughness, etc.), and whether or not various treatments are applied to the protective film 2. Depending on the material of the protective film 2, for example, a small average pore size, low porosity, and the application of a water-repellent or liquid-repellent treatment will affect the inherent contact angle θ of the protective film 2. M It can contribute to increasing [something].

[0103] The inherent contact angle θ of the protective film 2 when it is incorporated into the protective cover member 1. M For example, (I) the portion of the exposed surface 22 that coincides with the fixing portion 21 when viewed perpendicular to the main surface of the protective film 2 (e.g., the ventilation / sound permeability region 23), or (II) the exposed surface of the protective film 2 facing the adhesive layer 3, with respect to the contact angle θ. M This can be identified through evaluation.

[0104] A preferred example of the protective cover member 1 has at least one feature selected from the following features I to III. The preferred example may have at least two features selected from features I to III, or it may have all of features I to III. However, the protective cover member 1 is not limited to this preferred example. I: Intrinsic contact angle θ of protective film 2 M The temperature is 75 degrees or higher. II: The protective film 2 is a porous film or a microporous film, and its average pore diameter is less than 3 μm or within the preferred range described above. III: The adhesive layer 3 includes a thermosetting adhesive layer, the thermosetting adhesive layer is a layer formed from a thermosetting adhesive composition C, and the storage modulus G of the adhesive composition C at 130-170°C ’ is 1.0 × 10 3 Pa or higher, or within the preferred range described above.

[0105] The shape of the protective cover member 1 in Figures 1A to 1C is rectangular when viewed from a direction perpendicular to the main surface of the protective film 2. However, the shape of the protective cover member 1 is not limited to the above example. The shape may be a polygon including a square and a rectangle, a circle, or an ellipse when viewed from the above direction. The polygon may be a regular polygon. The corners of the polygon may be rounded.

[0106] The area of ​​the protective cover member 1 (the area when viewed from a direction perpendicular to the main surface of the protective film 2) is, for example, 175 mm². 2 The following is 150mm 2 Below, 125mm 2 Below, 100mm 2 Below, 75mm 2 Below, 50mm 2 Below, 25mm 2 Below, 20mm 2 Below, 15mm 2 Below, 10mm 2 Below, 7.5mm 2 Below, 5mm 2 Below, and even 2.5mm 2 The following may also apply. Protective cover members 1 with an area within the above range are suitable for placement on circuit boards and MEMS that typically have small-diameter openings, for example. The lower limit of the area of ​​the protective cover member 1 is, for example, 0.20 mm². 2 That concludes the explanation. However, the area of ​​the protective cover member 1 may be larger depending on the type of object it is placed on.

[0107] Examples of objects on which the protective cover member 1 is placed include semiconductor elements such as MEMS and circuit boards. In other words, the protective cover member 1 may be a component for semiconductor elements, circuit boards, or MEMS, with semiconductor elements, circuit boards, or MEMS as the target objects. MEMS may be non-sealed elements having ventilation holes on the surface of the package. Examples of non-sealed MEMS include various sensors that detect atmospheric pressure, humidity, gas, airflow, etc., and electroacoustic conversion elements such as speakers and microphones. Furthermore, the target objects are not limited to semiconductor elements and circuit boards after manufacturing, but may also be intermediate products of these elements or boards in the manufacturing process. In this case, the protective cover member 1 can protect the intermediate products in the manufacturing process. Examples of manufacturing processes include solder reflow processes, dicing processes, bonding processes, and mounting processes. Manufacturing processes, including solder reflow processes, may be processes carried out at high temperatures. High temperatures may be, for example, 200°C or higher, and may be 220°C or higher, 240°C or higher, or even 260°C or higher. The solder reflow process is typically carried out at around 260°C. However, the objects being processed are not limited to the examples given above.

[0108] Figure 4 shows an example of how the protective cover member 1 is positioned on the object in Figures 1A to 1C. In the example in Figure 4, the protective cover member 1 is positioned on the surface 53 of an object 51 which has an opening 52. The opening 52 is covered by the protective film 2 due to the positioning of the protective cover member 1. The adhesive layer 3 in Figure 4 is located on the side of the protective cover member 1 that is positioned on the surface 53 of the object 51, relative to the protective film 2. The protective cover member 1 is fixed to the surface 53 via the adhesive layer 3. In this example, the adhesive layer 3 constitutes the bonding surface 11 with the surface 53 of the object 51. Heat and pressure treatment such as hot pressing may be used to fix it to the surface 53.

[0109] The surface of the object on which the protective cover member 1 may be placed is, for example, the outer surface of the object. The surface may also be an internal surface of the object. The surface may be a flat surface or a curved surface. Furthermore, the opening in the object may be a recessed opening or a through-hole opening.

[0110] The protective cover member 1 may be used by being placed inside a semiconductor element such as a MEMS or a circuit board. An example of placement inside a MEMS is shown in Figure 5. Figure 5 shows an example of a MEMS equipped with the protective cover member 1 of this embodiment. The MEMS 61 in Figure 5 is a bottom-port (bottom-opening) type microphone element. The MEMS 61 comprises a substrate 62 having an opening 69, a MEMS die 63 having a diaphragm 64, and a cap (cover) 66. The opening 69 functions as a sound vent. Inside the MEMS 61 67, the protective cover member 1 is placed with the inner surface 68 of the substrate 62 as the placement surface, such that the opening 69 is covered by the protective film 2. The protective cover member 1 is fixed to the inner surface 68 via an adhesive layer 3. Thermal pressurization, such as hot pressing, may be used for fixing to the inner surface 68. The MEMS die 63 is bonded to the protective cover member 1, more specifically to the protective film 2, via an adhesive layer 65. The adhesive layer 65 is located on the opposite side of the protective film 2 from the adhesive layer 3 and is in contact with the protective film 2. Furthermore, the adhesive layer 65 overlaps with the fixing portion 21 of the protective film 2 when viewed from a direction perpendicular to the main surface of the protective film 2 (in the example in Figure 5, it coincides with the fixing portion 21).

[0111] The adhesive layer 65 is formed, for example, by applying an adhesive composition, which is a fluid 5, to the exposed surface 22 of the protective film 2. The adhesive composition for forming the adhesive layer 65 may be selected from the above-mentioned adhesive compositions that can form the adhesive layer 3. Since the MEMS die 63 is a fine component, an adhesive composition particularly suitable for coating a minute area, such as a liquid adhesive, may be used for the adhesive layer 65. The liquid adhesive is, for example, a low-viscosity adhesive composition using an alcohol such as methanol as a solvent. The viscosity (at 25°C) of the liquid adhesive is, for example, 0.1 to 500 Pa·s. The viscosity of the liquid adhesive can be evaluated, for example, by a Brookfield B viscometer. The liquid adhesive may contain an inorganic compound such as alumina as its main component, and may substantially not contain polymer components found in general adhesives. The protective cover member 1 of this embodiment, which has a protective film 2 having region A, is suitable for bonding with the MEMS die 63 via an adhesive layer 65 formed from a liquid adhesive. In this specification, the main component refers to the component present in the highest proportion. The content of the main component may be 50% by weight or more, 60% by weight or more, or even 70% by weight or more.

[0112] The MEMS61 may include any other components not described above.

[0113] The laminate 4 of the protective cover member 1 may include layers other than the protective film 2 and the adhesive layer 3. An example of a protective cover member 1 with further layers is shown in Figure 6.

[0114] The laminate 4 in Figure 6 further includes a base film 6 located on the side of the adhesive layer 3 relative to the protective film 2. The base film 6 can, for example, increase the rigidity of the protective cover member 1. Furthermore, when the protective cover member 1 is supplied by a member supply sheet, the pickability of the protective cover member 1 from the member supply sheet can be improved.

[0115] In Figure 6, the base film 6 is positioned on the side opposite to the protective film 2 relative to the adhesive layer 3. The base film 6 and the adhesive layer 3 are in contact with each other. However, the position of the base film 6 is not limited to the above example. The base film 6 may be positioned between the protective film 2 and the adhesive layer 3.

[0116] The laminate 4 in Figure 6 includes one base film 6. The laminate 4 may include two or more base films 6. The two or more base films 6 may be positioned between the protective film 2 and the adhesive layer 3, and on the side opposite to the protective film 2 relative to the adhesive layer 3.

[0117] The protective cover member 1 in Figure 6 can be positioned on the surface 53 of the object 51 by an additional adhesive layer provided on the side opposite to the adhesive layer 3 relative to the base film 6. The adhesive composition forming the additional adhesive layer can be selected from the adhesive compositions described above. The additional adhesive layer may be included in the laminate 4.

[0118] The material of the base film 6 can be selected from the materials exemplified as the material of the protective film 2. The base film 6 may be composed of a heat-resistant material. Examples of heat-resistant materials are as described above in the description of the base material 32.

[0119] Another example of a protective cover member 1 having further layers is shown in Figure 7. The laminate 4 in Figure 7 further comprises a cover film 7 located on the side opposite to the adhesive layer 3 relative to the protective film 2. The cover film 7 is placed on top of the protective film 2. Other layers may be placed between the cover film 7 and the protective film 2. The cover film 7 functions as a protective film that protects the protective film 2, for example, until the protective cover member 1 is placed on the object. The cover film 7 may be peeled off after the protective cover member 1 is placed on the object. The cover film 7 may cover the entire protective film 2 or a portion of it when viewed from a direction perpendicular to the main surface of the protective film 2. The cover film 7 can be placed on the protective film 2, for example, via an adhesive layer provided on the side of the cover film 7 that faces the protective film 2. This adhesive layer is preferably weakly tacky.

[0120] The cover film 7 in Figure 7 has tabs 71, which are portions that protrude outward from the outer circumference of the protective film 2 when viewed from a direction perpendicular to the main surface of the protective film 2. The tabs 71 can be used to peel off the cover film 7. However, the shape of the cover film 7 is not limited to the above example.

[0121] Examples of materials that make up the cover film 7 include metals, resins, and composite materials thereof. Specific examples of materials that can make up the cover film 7 are the same as specific examples of materials that can make up the base material 32.

[0122] The thickness of the cover film 7 is, for example, 200 to 1000 μm.

[0123] The protective cover member 1 can be manufactured, for example, by arranging an adhesive composition in a predetermined pattern on the main surface of a protective film 2 and forming an adhesive layer 3 from the arranged adhesive composition. The arranged adhesive composition may be a thermosetting adhesive composition or adhesive composition C. A heat-pressure treatment may be used to form the adhesive layer 3. According to the inventors' studies, the heat-pressure treatment is suitable for forming an adhesive layer 3 having a reduced area. The heat-pressure treatment can be carried out with the adhesive composition arranged on the main surface of the protective film 2. The temperature of the heat-pressure treatment may be, for example, 50 to 300°C or 50 to 250°C. The pressure may be, for example, 1 to 500 kPa or 1 to 100 kPa. Examples of heat-pressure treatments include hot pressing and hot lamination.

[0124] [Material supply sheet] An example of a component supply sheet of the present invention is shown in Figure 8. The component supply sheet 81 in Figure 8 comprises a base sheet 82 and a plurality of protective cover members 1 arranged on the base sheet 82. The component supply sheet 81 is a sheet for supplying the protective cover members 1. With the component supply sheet 81, for example, the protective cover members 1 can be efficiently supplied for a process in which they are placed on the surface of an object.

[0125] In the example shown in Figure 8, two or more protective cover members 1 are arranged on the base sheet 82. The number of protective cover members 1 arranged on the base sheet 82 may be one.

[0126] In the example shown in Figure 8, two or more protective cover members 1 are regularly arranged on the base sheet 82. More specifically, the protective cover members 1 are arranged such that, when viewed perpendicular to the surface of the base sheet 82, the center of each protective cover member 1 is located at an intersection (grid point) of a rectangular grid. However, the arrangement of the regularly arranged protective cover members 1 is not limited to the above example. The centers of each protective cover member 1 may be regularly arranged so that they are located at the intersections of various grids such as a square grid, a rhombic grid, or a diamond grid. Furthermore, the arrangement of the protective cover members 1 is not limited to the above example. For example, when viewed perpendicular to the surface of the base sheet 82, the protective cover members 1 may be arranged in a staggered pattern. The center of a protective cover member 1 can be determined as the centroid of the shape of the member 1 when viewed from a direction perpendicular to the surface of the base sheet 82.

[0127] Examples of materials constituting the base sheet 82 include paper, metal, resin, and composite materials thereof. Examples of metals include stainless steel and aluminum. Examples of resins include polyester such as PET, polyolefins such as polyethylene and polypropylene, and vinyl chloride (preferably flexible vinyl chloride). However, the materials constituting the base sheet 82 are not limited to the above examples.

[0128] The protective cover member 1 may be placed on the base sheet 82 via an adhesive layer (e.g., adhesive layer 3) provided on the member 1. In this case, the surface on the base sheet 82 on which the protective cover member 1 is placed may be treated with a release treatment to improve release from the base sheet 82. The release treatment can be carried out by known methods.

[0129] The protective cover member 1 may be placed on the base sheet 82 via an adhesive layer, typically a weak adhesive layer, provided on the surface on which the protective cover member 1 is placed on the base sheet 82.

[0130] The thickness of the base sheet 82 is, for example, 1 to 200 μm.

[0131] The base sheet 82 in Figure 8 is a single sheet with a rectangular shape. The shape of the single sheet base sheet 82 is not limited to the above example, and may be a polygon including a square and a rectangle, a circle, an ellipse, etc. When the base sheet 82 is a single sheet, the component supply sheet 81 can be distributed and used in a single sheet state. The base sheet 82 may also be in the shape of a strip, in which case the component supply sheet 81 will also be in the shape of a strip. The strip-shaped component supply sheet 81 can be distributed as a wound body wound around a core.

[0132] The component supply sheet 81 can be manufactured by placing the protective cover member 1 on the surface of the base sheet 82. [Examples]

[0133] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the examples shown below.

[0134] First, the evaluation method will be described.

[0135] [Weight average molecular weight] The weight-average molecular weight of the acrylic polymer was evaluated by gel permeation chromatography (GPC). GPC was performed using four columns (all manufactured by Tosoh Corporation): TSK G2000H HR, G3000H HR, G4000H HR, and GMH-H HR, connected in series. Tetrahydrofuran was used as the lysed molten egg solution, and the procedure was carried out at a flow rate of 1 mL / min, a temperature of 40°C, a sample concentration of 0.1% by weight, and an injection volume of 500 μL of tetrahydrofuran solution and sample. A differential refractometer was used as the detector.

[0136] [Glass transition temperature (Tg)] The Tg of the acrylic polymer was calculated from the peak of tanδ (= loss modulus / storage modulus) evaluated using a viscoelasticity analyzer (Rheometric Scientific, RSA-III) under measurement conditions of a heating rate of 10°C / min and a frequency of 1 MHz.

[0137] [Epoxy value] The epoxy value of the acrylic polymer was evaluated in accordance with the provisions of JIS K7236. Specifically, the following procedure was followed: 4 g of the acrylic polymer to be evaluated was weighed into a 100 mL conical flask, and dissolved in 10 mL of chloroform. Then, 30 mL of acetic acid, 5 mL of tetraethylammonium bromide, and 5 drops of crystal violet indicator were added, and the mixture was titrated with 0.1 mol / L perchloric acid acetic acid normal solution while stirring with a magnetic stirrer. A blank test was performed in the same manner, and the epoxy value was calculated using the following formula. Formula: Epoxy value = [(VV B ) × 0.1 × F] / 4 (g) V B : Volume (mL) of perchloric acid acetic acid normal solution required for the blank test V: Volume (mL) of perchloric acid acetate normal solution required for titration of the sample. F: Factor of perchloric acid acetic acid standard solution

[0138] [Storage modulus G at 130~170℃] ’ ] For thermosetting resin compositions, the storage modulus G at 130-170°C. ’ The evaluation was performed as follows: First, the prepared thermosetting resin composition was applied to the surface of a PET sheet (thickness 50 μm) that had been treated with a silicone release agent to form a coating film (thickness 25 μm). The coating film was dried by heating at 130°C for a short time (2 minutes), under conditions where the thermosetting of the composition was almost ineffective, to form a film. Next, the obtained film was peeled from the PET film and cut into pieces 22.5 mm in length and 10 mm in width to form test specimens. Next, the test specimens were heated from 0°C to 260°C at a heating rate of 10°C / min using a forced vibration type solid viscoelasticity measuring device (Rheometric Scientific, RSA-III) to determine the storage modulus G at 130-170°C. ’ The following was evaluated. The measurement direction (vibration direction) of the test specimen was the longitudinal direction, and the vibration frequency was set to 1 Hz.

[0139] [Storage modulus G at 130-170°C or 250°C after heat curing] ’ ] For thermosetting resin compositions, the storage modulus G' at 130-170°C or 250°C after heat curing was evaluated as follows. First, the storage modulus G ’ Similar to the evaluation, a coating film of the thermosetting resin composition was formed on a PET film. Next, the coating film was cured into a cured film by curing it at 170°C for 60 minutes, which are the conditions under which the thermosetting of the above composition proceeds. Next, the obtained cured film was peeled off the PET film and cut into pieces 22.5 mm in length and 10 mm in width to make test specimens. Next, the test specimens were heated from 0°C to 260°C at a heating rate of 10°C / min using the above solid viscoelasticity measuring device to obtain the storage modulus G' at 130-170°C and the storage modulus G' at 250°C. ’ The following was evaluated. The measurement direction (vibration direction) of the test specimen was the longitudinal direction, and the vibration frequency was set to 1 Hz.

[0140] [Air permeability in the thickness direction] The air permeability in the thickness direction of the protective film was determined as air permeability (Gurley air permeability) in accordance with the air permeability measurement method B (Gurley method) specified in JIS L1096:2010.

[0141] [Average pore diameter] The average pore size of the protective film was determined using an Automated perm porometer manufactured by Porous Materials Inc., which is capable of measurement in accordance with ASTM F316-86.

[0142] [Contact angle θ for methanol] M ] The contact angle θ with methanol for the main surface of the prepared protective film and the exposed surface of the protective film in the laminate of the protective film and the adhesive layer (corresponding to the exposed surface of the fixing portion of the protective film provided by the protective cover member) MThe evaluation was performed using the Contact Angle System OCA 30 from DataPhysics Instruments, which allows for evaluation in accordance with the static droplet method specified in JIS R3257. However, the evaluation was carried out using a 2 μL methanol droplet instead of a water droplet. The evaluation temperature was 25°C.

[0143] [Evaluation of the spread of fluid 5] The extent to which the fluid 5 spread over the exposed surface of the protective film in the laminate of the protective film and adhesive layer was evaluated as follows. As the fluid 5, a liquid adhesive was prepared by mixing adhesive (ThreeBond, TB3732) and methanol in a weight ratio of 3:5. Next, 2 μL of the liquid adhesive was dropped onto the exposed surface of the protective film, and the height of the droplet immediately after dropping was evaluated using the Contact Angle System OCA 30 described above. If the droplet height (corresponding to the distance from the exposed surface to the top of the droplet) remained above 0.05 mm, it was judged as excellent (○), and if it fell below 0.05 mm, it was judged as poor (×). The evaluation was performed at 25°C.

[0144] [Preparation of protective film] The following PTFE films a to f were prepared as protective layers.

[0145] (PTFE membrane a) 100 parts by weight of PTFE fine powder (AGC Inc., Fluon CD123E) was uniformly mixed with 20 parts by weight of liquid lubricant (n-dodecane, Japan Energy Co., Ltd.). This mixture was compressed in a cylinder and then extruded in a ram extruder to obtain a sheet-like molded body that stretches in the longitudinal direction. This sheet-like molded body, with the liquid lubricant still present, was passed between metal rolling rolls and rolled to a thickness of 0.2 mm. The liquid lubricant was then removed by heating the sheet-like molded body to 150°C, and the sheet-like molded body was dried. Subsequently, the sheet-like molded body was stretched at 300°C in the longitudinal direction by a factor of 2.5, and then stretched at 200°C in the width direction by a factor of 20. Finally, it was fired at 400°C, a temperature above the melting point of PTFE, to obtain a film thickness of 15 μm and a surface density of 5 g / m². 2 A PTFE film a with a thickness-direction air permeability of 1.3 seconds / 100 mL and an average pore size of 1 μm was obtained.

[0146] (PTFE membrane b) A PTFE film a was subjected to a liquid-repellent treatment to obtain a PTFE film b. The liquid-repellent treatment was performed by immersing PTFE film a in a liquid-repellent solution (a solution of Shin-Etsu Chemical's X-70-029C, a liquid repellent, diluted with Shin-Etsu Chemical's FS thinner to a concentration of 1.5% by weight) for 3 seconds, removing it, and letting it dry at room temperature for 30 minutes. The film thickness, surface density, air permeability in the thickness direction, and average pore size of PTFE film b were 15 μm and 5.5 g / m², respectively. 2 The values ​​were 4.0 seconds / 100 mL and 1 μm.

[0147] (PTFE membrane c) A dispersion of PTFE particles (PTFE particle concentration 40% by mass, average particle size of PTFE particles 0.2 μm, containing 6 parts by mass of nonionic surfactant per 100 parts by mass of PTFE) was prepared by adding 1 part by mass of a fluorine-based surfactant (DIC, Megafac F-142D) per 100 parts by mass of PTFE. Next, a coating film (20 μm thick) of the PTFE dispersion with the added fluorine-based surfactant was formed on the surface of a strip-shaped polyimide substrate (125 μm thick). The coating film was formed by immersing the polyimide substrate in the PTFE dispersion and then removing it. Next, the entire substrate and coating film were heated to form a PTFE cast film. The heating was performed in two stages: a first heating (100°C, 1 minute) followed by a second heating (390°C, 1 minute). The first heating removed the dispersion medium contained in the coating film, and the second heating promoted the formation of a cast film based on the binding of PTFE particles contained in the coating film. After repeating the above immersion and subsequent heating process two more times, the formed PTFE cast film (25 μm thick) was peeled off the polyimide substrate. Next, the peeled cast film was rolled in the MD direction (longitudinal direction) and then stretched in the TD direction (width direction). Rolling in the MD direction was performed by roll rolling. The rolling ratio (area ratio) was 2.0 times, and the temperature (roll temperature) was 170°C. Stretching in the TD direction was performed by a tenter stretcher. The stretching ratio in the TD direction was 2.0 times, and the temperature (temperature of the stretching atmosphere) was 300°C. In this way, a film thickness of 10 μm and a surface density of 14 g / m² were obtained. 2A PTFE film c with a thickness-direction air permeability of 100 seconds / 100 mL and an average pore size of 0.1 μm was obtained.

[0148] (PTFE membrane d) For the PTFE film d, we prepared NTF1033 manufactured by Nitto Denko Corporation. The thickness of the PTFE film d was 20 μm, and the surface density was 4.4 g / m². 2 The air permeability in the thickness direction was 0.6 seconds / 100 mL, and the average pore size was 3 μm.

[0149] (PTFE membrane e) 100 parts by weight of PTFE fine powder (Daikin Industries, Ltd., Polyflon F101HE) was uniformly mixed with 20 parts by weight of liquid lubricant (n-dodecane, Japan Energy Co., Ltd.). This mixture was compressed in a cylinder and then extruded in a ram extruder to obtain a sheet-like molded body that stretches in the longitudinal direction. This sheet-like molded body, containing the liquid lubricant, was passed between metal rolling rolls and rolled to a thickness of 0.2 mm. The liquid lubricant was then removed by heating the sheet-like molded body to 150°C, and the sheet-like molded body was dried. Subsequently, the sheet-like molded body was stretched at a ratio of 9 times in the longitudinal direction at 290°C, and then stretched at a ratio of 53 times in the width direction at 150°C. Finally, it was fired at a temperature above the melting point of PTFE, 400°C, to obtain a film thickness of 3 μm and a surface density of 1.5 g / m². 2 A PTFE film e with a thickness-direction air permeability of 1.5 seconds / 100 mL and an average pore size of 0.35 μm was obtained.

[0150] (PTFE membrane) A PTFE film e was subjected to a liquid-repellent treatment to obtain a PTFE film f. The liquid-repellent treatment was performed by immersing the PTFE film e in a liquid-repellent solution (a solution of Shin-Etsu Chemical's X-70-043, a liquid repellent, diluted with Shin-Etsu Chemical's FS thinner to a concentration of 1.5% by weight) for 3 seconds, removing it, and drying it at room temperature. The film thickness, surface density, air permeability in the thickness direction, and average pore size of the PTFE film f were 3 μm and 1.7 g / m², respectively. 2 The values ​​were 2.0 seconds / 100 mL and 0.38 μm.

[0151] Contact angle θ with respect to the main surface of each PTFE film M(The intrinsic contact angle θ of the PTFE film) M The evaluation results are shown in Table 1 below.

[0152] [Table 1]

[0153] [Preparation of the adhesive composition] The following compositions a to c were prepared as thermosetting adhesive compositions to be used in the adhesive layer.

[0154] (composition a) As acrylic polymer D, 9 parts by weight of butyl acrylate-ethyl acrylate-acrylonitrile-acrylic acid copolymer (manufactured by Negami Kogyo, weight-average molecular weight 800,000, acid value 5 mg KOH / g, Tg -15℃), and as thermosetting resins, 26 parts by weight of phenol resin (manufactured by Meiwa Kasei, MEH7851SS) and 25 parts by weight of epoxy resin (a mixture of Mitsubishi Chemical's YL980 and DIC's N-665-EXP-S in a 1:1 weight ratio) were dissolved in methyl ethyl ketone, and 40 parts by weight of spherical silica (manufactured by Admatex, SE2050) with an average particle size of 500 nm were dispersed to prepare a thermosetting resin composition a with a concentration of 23.6% by weight.

[0155] (composition b) A thermosetting resin composition b with a concentration of 23.6% by weight was prepared in the same manner as composition a, except that butyl acrylate-ethyl acrylate-acrylonitrile-acrylic acid copolymer (manufactured by Negami Kogyo, weight-average molecular weight 400,000, acid value 5 mg KOH / g, Tg -15℃) was used as the acrylic polymer D, and MEH7800H manufactured by Meiwa Kasei was used as the phenolic resin, and the materials were blended so that the content of acrylic polymer D, phenolic resin, epoxy resin, and silica in the prepared composition was 11% by weight, 32% by weight, 32% by weight, and 25% by weight, respectively.

[0156] (composition c) A thermosetting resin composition c with a concentration of 23.6% by weight was prepared in the same manner as composition a, except that butyl acrylate-ethyl acrylate-acrylonitrile-glycidyl methyl acrylate copolymer (manufactured by Negami Kogyo, weight-average molecular weight 800,000, epoxy value 0.4 eq / kg, Tg 0℃) was used as the acrylic polymer D, and the epoxy resin was not used, and the materials were blended so that the content of acrylic polymer D, phenol resin, and silica in the prepared composition was 52% by weight, 6% by weight, and 42% by weight, respectively.

[0157] The evaluation results for the storage modulus G' at 130-170°C, the storage modulus G' at 130-170°C after heat curing, and the storage modulus G' at 250°C after heat curing for adhesive compositions a to c are shown in Table 2 below.

[0158] [Table 2]

[0159] [Fabrication of a laminate consisting of a protective film and an adhesive layer] Assuming a fixing section for the protective film on a protective cover component, laminates of the protective film and adhesive layer (Samples 1-14) were fabricated as follows. A hot press was used for fabrication. Specifically, the process is as follows:

[0160] (Sample 1) First, composition a was applied to the surface of a PET sheet (50 μm thick) that had been treated with a silicone release agent to form a coating film (20 μm thick). Next, the coating film was dried by heating at 130°C for 2 minutes to form a film. Then, the obtained film was bonded to a PTFE film a as a protective film, and the resulting laminate was cut into a 20 mm × 20 mm square. Next, the entire laminate was sandwiched between a pair of polyimide films (25 μm thick), and it was hot-pressed in the thickness direction using a hot press machine (Tester Industries Co., Ltd., high-precision hot press SA-401-M). The hot-pressing conditions were a temperature of 130°C, a pressure of 20 kPa, and a time of 13 seconds. After the hot-pressing was completed, the polyimide films were peeled off to obtain a laminate of the protective film and the adhesive layer.

[0161] (Samples 2-14) Samples 2 to 14, which are laminates of a protective film and an adhesive layer, were obtained in the same manner as Sample 1, except that the PTFE film used as the protective film and the adhesive composition were selected as shown in Table 3 below.

[0162] [Table 3]

[0163] The evaluation results for each sample are shown in Table 4 below.

[0164] [Table 4] [Industrial applicability]

[0165] The protective cover member of the present invention can be used, for example, in the manufacture of semiconductor elements such as MEMS and / or circuit boards equipped with such elements.

Claims

1. A protective cover member that is placed on the surface of an object having an opening, The laminate includes a protective film having a shape that covers the opening when the protective cover member is placed on the surface, and an adhesive layer. When the portion of the protective film that coincides with the adhesive layer when viewed from a direction perpendicular to the main surface of the protective film is defined as the fixing portion of the protective film, the exposed surface of the protective film opposite to the side facing the adhesive layer is, Region A, which overlaps with the fixed portion when viewed from the aforementioned vertical direction and has a contact angle with methanol of 55 degrees or more. It has, The adhesive layer includes a layer formed from a thermosetting adhesive composition. A protective cover member wherein the storage modulus of the thermosetting adhesive composition is 1.0 × 10³ Pa or more at 130 to 170°C.

2. The protective cover member according to claim 1, wherein the entire exposed surface on the opposite side of the fixed portion has a contact angle with methanol of 55 degrees or more.

3. The protective cover member according to claim 1, wherein the fixing portion is located on the peripheral edge of the protective film when viewed from the vertical direction.

4. The protective cover member according to claim 1, wherein the adhesive layer is in contact with the protective film.

5. The protective cover member according to claim 1, wherein the adhesive layer is located on the side of the protective cover member that faces the surface of the object, relative to the protective film.

6. The storage modulus of the thermosetting adhesive composition after heat curing is 1.0 × 10⁻¹⁰ at 130 to 170°C. 8 The protective cover member according to claim 1, wherein the pressure is Pa or less.

7. When viewed from a direction perpendicular to the main surface of the protective film, The adhesive layer is positioned at the periphery of the protective film. The length L of the shortest line segment from the center of the protective film to the outer circumference of the protective film. 1 The length L of the portion of the shortest line segment that overlaps with the adhesive layer. 2 Ratio L 2 / L 1 The protective cover member according to claim 1, wherein the value is 0.5 or less.

8. The protective cover member according to claim 1, wherein the protective film has breathability in the thickness direction.

9. The protective film includes a porous film or a microporous film. The protective cover member according to claim 1, wherein the average pore diameter of the porous membrane and the microporous membrane is 0.01 μm or more and less than 3 μm.

10. The protective cover member according to claim 1, wherein the protective film includes a polytetrafluoroethylene film.

11. The area of ​​the protective film is 175 mm². 2 The protective cover member according to claim 1, wherein the following applies:

12. The protective cover member according to claim 1, wherein the laminate further includes a base film located on the side of the adhesive layer relative to the protective film.

13. A protective cover member according to claim 1, for use in a micro-electromechanical system (MEMS).

14. The protective cover member according to claim 13, which is used by being placed inside the MEMS.

15. A protective cover member disposed on the surface of an object having an opening, The laminate includes a protective film having a shape that covers the opening when the protective cover member is placed on the surface, and an adhesive layer. When the portion of the protective film that coincides with the adhesive layer when viewed from a direction perpendicular to the main surface of the protective film is defined as the fixing portion of the protective film, the exposed surface of the protective film opposite to the side facing the adhesive layer is, Region A, which overlaps with the fixed portion when viewed from the aforementioned vertical direction and has a contact angle with methanol of 55 degrees or more. It has, The adhesive layer includes a layer formed from a thermosetting adhesive composition. A protective cover member wherein the storage modulus of the thermosetting adhesive composition after heat curing is 1.0 × 10⁸ Pa or less at 130 to 170°C.

16. The device comprises a base sheet and one or more protective cover members arranged on the base sheet, The protective cover member is a member supply sheet, which is a protective cover member according to any one of claims 1 to 15.

17. A micro-electromechanical system comprising a protective cover member according to any one of claims 1 to 15.

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