Protective cover member and member supply sheet

Abstract

The protective cover member provided is a protective cover member arranged on a surface of an object having a surface with an opening, the protective cover member is composed of a laminate, the laminate includes a protective film and an adhesive layer, the protective film has a shape covering the opening when the member is arranged on the surface. The adhesive layer includes a cured adhesive layer of a silicone adhesive composition including an addition reaction curing silicone adhesive. The protective cover member is a member that can suppress deformation and peeling from the arrangement surface even at high temperatures such as reflow soldering.

Description

Technical Field

[0001] The present invention relates to a protective cover member disposed on a surface of an object having a surface with an opening, and a member supplying belt for supplying the member. Background Art

[0002] It is known that there is a protective cover component that is arranged on a surface of an object having an opening to prevent foreign matter from invading the opening. The protective cover component usually comprises: a protective film that prevents foreign matter from invading the opening when the component is arranged on the surface, and an adhesive layer for fixing the component to the surface. Patent document 1 discloses a component that comprises: a porous membrane having polytetrafluoroethylene (hereinafter referred to as "PTFE") as a main component, allowing gas and / or sound to pass through and preventing foreign matter such as water droplets from passing through; and a heat-resistant double-sided adhesive sheet that is arranged in a restricted area on at least one main surface of the porous membrane in order to fix the porous membrane to other components. In Patent document 1, an attempt is made to ensure the heat resistance of the component to high temperatures during reflow soldering by focusing on the base material of the double-sided adhesive sheet used to fix the component to the surface of a circuit substrate as an object.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2007-81881 Summary of the invention

[0006] Problem that the invention aims to solve

[0007] In recent years, there has been a demand for configuring a protective cover member for the openings of micro products such as micro-electro-mechanical systems (hereinafter referred to as "MEMS"). In addition, there is also a demand for configuring a protective cover member not only for the outer surface but also for the inner surface of the product. In order to meet such a demand, the current situation is that the protective film is being reduced in area. In this case, in order to ensure the air permeability and / or sound permeability through the protective film as much as possible, it is only possible to reduce the area of ​​the adhesive layer that hinders the air permeability and sound permeability, for example, to reduce the width of the adhesive layer arranged on the peripheral portion of the protective film. According to the research of the inventors of the present invention, when the area of ​​the adhesive layer is reduced, there is a tendency for the protective cover member to deform and peel off from the above-mentioned surface (arrangement surface) under high temperatures such as reflow soldering. The above situation is not taken into account in Patent Document 1.

[0008] An object of the present invention is to provide a protective cover member which can suppress deformation and peeling from a placement surface even under high temperature conditions such as reflow soldering.

[0009] Solutions for solving problems

[0010] The present invention provides a protective cover member, which is arranged on the surface of an object having a surface with an opening.

[0011] The protective cover member is composed of a laminated body including a protective film and an adhesive layer, wherein the protective film has a shape that covers the opening when the member is arranged on the surface.

[0012] The adhesive layer comprises a cured adhesive layer of a silicone adhesive composition containing an addition reaction-curable silicone adhesive.

[0013] According to another aspect, the present invention provides a member supply sheet comprising: a base sheet, and one or more protective cover members disposed on the base sheet.

[0014] The aforementioned protective cover member is the protective cover member of the present invention described above.

[0015] Effects of the Invention

[0016] According to the research of the inventors, the shrinkage of the adhesive layer at high temperature is one of the causes of the above-mentioned deformation and peeling. In the protective cover member of the present invention, the adhesive layer has a specific silicone-based cured adhesive layer. The adhesive layer shrinks less at high temperatures. Therefore, the above-mentioned deformation and peeling at high temperatures can be suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1A This is a cross-sectional view schematically showing an example of the protective cover member of the present invention.

[0018] Figure 1B When viewed from the adhesive layer 3 side Figure 1A A top view of the protective cover component 1.

[0019] Figure 2 This is a schematic diagram showing an example of the arrangement of the protective cover member of the present invention on an object.

[0020] Figure 3 This is a cross-sectional view schematically showing an example of the protective cover member of the present invention.

[0021] Figure 4A This is a cross-sectional view schematically showing an example of the protective cover member of the present invention.

[0022] Figure 4B This is a cross-sectional view schematically showing an example of the protective cover member of the present invention.

[0023] Figure 5 This is a cross-sectional view schematically showing an example of the protective cover member of the present invention.

[0024] Figure 6 This is a cross-sectional view schematically showing an example of the protective cover member of the present invention.

[0025] Figure 7 This is a plan view schematically showing an example of the member supplying sheet of the present invention.

[0026] Figure 8 The figures show the appearance of each example and comparative example sample after heat treatment. DETAILED DESCRIPTION

[0027] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments.

[0028] [Protective cover member]

[0029] An example of the protective cover member of the present invention is shown in Figure 1A and Figure 1B . Figure 1B When viewed from the adhesive layer 3 side Figure 1A A top view of the protective cover component 1. Figure 1A Shown in Figure 1B Section AA. The protective cover member 1 is a member configured on the surface (configuration surface) of an object having a surface with an opening. By configuring the protective cover member 1 to the configuration surface, for example, it is possible to prevent foreign matter from intruding into the above-mentioned opening and / or from the above-mentioned opening, in other words, it is possible to prevent foreign matter from intruding through the above-mentioned opening. The protective cover member 1 can be a member configured on the surface of an object having a surface with an opening to prevent foreign matter from intruding into the above-mentioned opening. The protective cover member 1 is composed of a stack 4, and the stack 4 includes a protective film 2 and an adhesive layer 3. The protective film 2 has a shape that covers the above-mentioned opening when the protective cover member 1 is configured on the above-mentioned surface. The adhesive layer 3 is located on one main surface side of the protective film 2. The adhesive layer 3 is bonded to the protective film 2. The protective cover member 1 can be fixed to the configuration surface of the object using the adhesive layer 3.

[0030] The adhesive layer 3 includes a cured adhesive layer 11 of a silicone adhesive composition A (hereinafter referred to as "composition A") containing an addition reaction curable silicone adhesive. The cured adhesive layer 11 is a cured layer of the composition A and has adhesive properties. The cured adhesive layer 11 is formed by curing the composition A. Figure 1A and Figure 1B The adhesive layer 3 includes a cured adhesive layer 11. The cured adhesive layer 11 is in contact with the protective film 2. In addition, the cured adhesive layer 11 will become the bonding surface 12 of the protective cover member 1 with respect to the configuration surface of the object. The cured adhesive layer 11 and the adhesive layer 3 including the cured adhesive layer 11 shrink less at high temperatures. Therefore, deformation of the protective film 2 caused by shrinkage and peeling of the adhesive layer 3 from the protective film 2 and / or the configuration surface can be suppressed.

[0031] Composition A contains an addition reaction curing type silicone adhesive, preferably contains an addition reaction curing type silicone adhesive as a main component. In this specification, the main component refers to the component with the largest content. The content of the main component is, for example, 50% by weight or more, and can be 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, and further 99% by weight or more. Composition A can be formed by an addition reaction curing type silicone adhesive. Composition A preferably does not contain a peroxide curing type silicone adhesive. The cured adhesive layer of the peroxide curing type silicone adhesive shrinks greatly at high temperatures.

[0032] It is speculated that the difference in shrinkage rate at high temperature between the cured adhesive layer of the addition reaction curing type silicone adhesive and the cured adhesive layer of the peroxide curing type silicone adhesive is based on the difference in the distribution state of the crosslinking points caused by the difference in reaction mechanism. For the addition reaction curing type, the addition reaction groups that become crosslinking points are uniformly present in the composition, and three-dimensional crosslinking based on the hydrogen silane compound with a large number of crosslinking points is performed, so the distribution of the crosslinking points of the cured adhesive layer becomes relatively uniform. On the other hand, for the peroxide curing type, among the multiple functional groups that the silicone molecule can have, the functional groups that generate free radicals react randomly and competitively to become crosslinking points, so the position and number of crosslinking points vary depending on the silicone molecule, and the distribution of the crosslinking points of the cured adhesive layer becomes more random. It is speculated that this difference leads to the difference in shrinkage rate at high temperature.

[0033] The composition A generally comprises: an organosilicon compound having an addition reaction group (ingredient A), an organosilicon resin (ingredient B), a hydrosilane compound (ingredient C) and a catalyst (ingredient D).

[0034] Examples of the organosilicon compound (component A) having an addition reaction group are organopolysiloxanes having addition reaction groups and partial condensates thereof. The organopolysiloxane may be any of monoorganopolysiloxane, diorganopolysiloxane and triorganopolysiloxane, preferably at least one selected from monoorganopolysiloxane and diorganopolysiloxane, and more preferably diorganopolysiloxane. Examples of the organic group of the organopolysiloxane are hydrocarbon groups having 1 to 8 carbon atoms, preferably hydrocarbon groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 1 to 4 carbon atoms (which may be linear or branched). A typical example of the organic group is a methyl group. A portion of the organic group may be substituted with a hydroxyl group. Examples of the addition reaction group are monovalent organic groups containing alkenyl groups, typical examples of which are vinyl and allyl groups, preferably vinyl groups. The addition reaction group is usually present at at least one end of the molecule of component A, and may also be present at both ends. Specific examples of component A are vinyldimethylpolysiloxane, vinyldiethylpolysiloxane, vinylisopropylpolysiloxane, and vinylphenylmethylsiloxane. The content of the addition reaction group in Component A is, for example, 0.0005 mol or more and 0.5 mol or less relative to 100 g of the organosilicon compound. Component A usually does not have a Q unit (SiO 2 ) and a Si—H group.

[0035] The weight average molecular weight of component A is, for example, 100,000 to 1,000,000, or 100,000 to 500,000. Component A may be in an oily state or in a raw rubber state (silicone rubber).

[0036] The content of the component A in the composition A is, for example, 20 to 80% by weight, or 30 to 70% by weight.

[0037] Composition A may contain two or more components A.

[0038] Examples of the silicone resin (ingredient B) are those having a Q unit and an M unit selected from the group consisting of R3SiO 1 / 2 ), D unit (R2SiO) and T unit (RSiO 3 / 2 ) and its partial condensate. Examples of R in M ​​unit, D unit and T unit are independently a hydrocarbon group with 1 to 8 carbon atoms, preferably a hydrocarbon group with 1 to 4 carbon atoms, and more preferably an alkyl group with 1 to 4 carbon atoms (which may be linear or branched). A typical example of R is methyl. A part of R may be substituted with hydroxyl group. Component B usually does not have an addition reaction group. Component B is preferably a so-called MQ resin composed of M unit and Q unit. R of the M unit in the MQ resin may be methyl.

[0039] The content ratio (molar ratio) of the M unit and the Q unit in the MQ resin is represented by M unit:Q unit, and is, for example, 0.3:1 to 1.5:1, or 0.5:1 to 1.3:1.

[0040] The weight average molecular weight of component B is, for example, 1,000 to 10,000, or 3,000 to 8,000.

[0041] The content of the component B in the composition A is, for example, 20 to 80% by weight, or 30 to 70% by weight.

[0042] The composition A may contain two or more components B.

[0043] The blending ratio (mass ratio) of component A and component B in composition A is represented by component A:component B, and is, for example, 20:80 to 80:20, or 25:75 to 50:50.

[0044] The hydrogen silane compound (component C) is a component having a Si-H group and reacting with the addition reaction group of component A to form a crosslinked structure. Examples of component C are hydrogen organopolysiloxane and partial condensates thereof. The hydrogen organopolysiloxane may be any of hydrogen monoorganopolysiloxane and hydrogen diorganopolysiloxane. Examples of organic groups, including preferred embodiments, are the same as those of the organic groups of component A. A portion of the organic group may be substituted with a hydroxyl group. Specific examples of component C are hydrogen monomethyl polysiloxane and hydrogen dimethyl polysiloxane, which may be a copolymer of hydrogen monomethyl siloxane and hydrogen dimethyl siloxane.

[0045] The weight average molecular weight of component C is, for example, 100 to 10000, or 100 to 1000. Component C may be in an oily state or in a raw rubber state (silicone rubber).

[0046] Component C is preferably blended into composition A such that the molar ratio of Si—H groups in component C to addition reaction groups contained in composition A, such as alkenyl-containing monovalent organic groups, is, for example, 0.5 to 20, particularly 0.8 to 15.

[0047] Composition A may contain two or more components C.

[0048] The catalyst (component D) is a component that accelerates the curing reaction of the composition A. The catalyst is typically a catalyst containing a platinum group element, preferably a platinum-based catalyst. The platinum group element contained in the component D remains in the cured adhesive layer 11 .

[0049] The content of the component D in the composition A is, for example, 5 to 500 ppm (weight basis, the same applies hereinafter), and can be 10 to 200 ppm.

[0050] Composition A may contain other components than those described above as long as the effects of the present invention can be obtained. Examples of other components include organosilicon compounds other than component A, component B, and component C, reaction control agents, antioxidants, and ultraviolet absorbers.

[0051] As the addition reaction curing type silicone adhesive, a commercially available addition reaction curing type silicone adhesive can be used. An addition reaction curing type silicone adhesive not included in the above examples may also be used.

[0052] For the cured adhesive layer 11, the shrinkage X at 260°C in at least one direction within the plane can be 15% or less. The shrinkage X can be 14% or less, 13% or less, 12% or less, 11% or less, and further 10% or less. The lower limit of the shrinkage X is, for example, 0.01% or more. The cured adhesive layer 11 can have a shrinkage X within the above range in at least two or more directions within the plane, and can have a shrinkage X within the above range in all directions within the plane. When the cured adhesive layer 11 is formed, when the composition A is applied in one direction to the surface of a base sheet such as a substrate 13A described later, the cured adhesive layer 11 can have a shrinkage X within the above range in MD (coating direction of the composition A) and / or TD (direction perpendicular to MD within the plane of the cured adhesive layer 11). The shrinkage rate X can be obtained as follows: the dimension in the above direction before the heat treatment in a state formed on a polyimide substrate (thickness 25 μm) in a heating tank maintained at 260° C. for 1 minute is defined as D0, and the dimension in the above direction after the heat treatment is defined as D1, and the shrinkage rate X can be obtained by the formula: (D0-D1) / D0×100(%). It should be noted that the measurement of the dimensions D0 and D1 is carried out in an environment of a temperature of 25° C.±5° C. and a humidity of 50±5%RH.

[0053] The gel fraction of the cured adhesive layer 11 is, for example, 25 to 80% by weight. The gel fraction is preferably 25 to 65% by weight, 30 to 60% by weight, and further 35 to 55% by weight. When the gel fraction is in the above-mentioned preferred range, the initial adhesion (anchoring property) of the cured adhesive layer 11 to the PTFE membrane and / or the adhesion after the heat treatment at 260°C can be improved. A PTFE membrane headed by a PTFE stretched porous membrane is sometimes used in the protective film 2. However, PTFE is a substance with low adhesion. In the protective cover member 1 to which the cured adhesive layer 11 is bonded to the protective film 2, if the gel fraction of the cured adhesive layer 11 is in the above-mentioned preferred range, based on the improved adhesion, the deformation of the protective cover member 1 at high temperature and the suppression of the peeling of the protective film 2 and the adhesive layer 3 become reliable.

[0054] The gel fraction of the cured adhesive layer 11 can be obtained by the following method. After wrapping a test piece of about 0.1 g taken from the cured adhesive layer 11 of the evaluation object in a PTFE stretched porous film with an average pore size of 0.2 μm (for example, NTF1122 manufactured by Nitto Denko), it is tied with a kite string to serve as a measurement sample. Next, the weight of the measurement sample (weight before immersion C) is measured. The weight before immersion C is equivalent to the total weight of the test piece, the PTFE stretched porous film and the kite string. Separately from the above, the bag weight B, which is the total weight of the PTFE stretched porous film and the kite string, is measured in advance. Next, the measurement sample is placed in a container with an internal volume of 50 mL filled with toluene and left to stand at 23°C for 7 days. Next, after cleaning the container together with the measurement sample with ethyl acetate, the measurement sample is taken out, moved to an aluminum cup, and dried at 130°C for 2 hours to remove the ethyl acetate. Next, the weight of the measurement sample (weight after immersion A) is measured. The gel fraction can be calculated by the formula: gel fraction (weight %) = (weight after immersion A - bag weight B) / (weight before immersion C - bag weight B) × 100. The weight measurement was carried out under the environment of temperature 25±5°C and humidity 50±5%RH.

[0055] The initial bonding force of the cured adhesive layer 11 to the PTFE membrane is, for example, 1.5 N / 20 mm or more, and can be 1.7 N / 20 mm or more, 1.8 N / 20 mm or more, 2.0 N / 20 mm or more, 2.5 N / 20 mm or more, 3.0 N / 20 mm or more, 3.5 N / 20 mm or more, and further 4.0 N / 20 mm or more. The upper limit of the initial bonding force is, for example, 100 N / 20 mm or less. The bonding force to the PTFE membrane after heat treatment (260° C., 1 minute) is, for example, 1.5 N / 20 mm or more, and can be 1.7 N / 20 mm or more, 1.8 N / 20 mm or more, 2.0 N / 20 mm or more, 2.4 N / 20 mm or more, 2.5 N / 20 mm or more, 3.0 N / 20 mm or more, 3.5 N / 20 mm or more, and further 4.0 N / 20 mm or more. The upper limit of the adhesive force is, for example, 100 N / 20 mm or less.

[0056] The elastic modulus (storage modulus G') of the cured adhesive layer 11 at 250°C is, for example, 5.0×10 4 Pa or above, it can be 5.5×10 4 Pa or above, 6.0×10 4 Pa or more, and 6.5×10 4 Pa or more. The upper limit of the elastic modulus at 250°C is, for example, 1.0×10 8 The elastic modulus can be measured by the following method using a rheometer. The cured adhesive layer 11 to be measured is cut out so that the surface area becomes 75 mm2 Next, the sample was subjected to a temperature rise measurement from a measurement start temperature of 25°C using a rheometer (e.g., Advanced Rheometric Expansion System (ARES) manufactured by Rheometric Scientific) under the conditions of a shear mode, a frequency of 1 Hz, and a temperature rise rate of 5°C / min, to determine the elastic modulus when the sample reached 250°C.

[0057] Figure 1B The adhesive layer 3 and the cured adhesive layer 11 are bonded to the protective film 2. Among them, other layers may be arranged between the adhesive layer 3 and / or the cured adhesive layer 11 and the protective film 2. The shrinkage of the cured adhesive layer 11 may affect other layers included in the laminate 4. Therefore, even when other layers are arranged therebetween, the effect of the present invention can be obtained.

[0058] Will Figure 1A and Figure 1B An example of the configuration of the protective cover member to the object is shown in Figure 2 . Figure 2 In the example of FIG. 1 , a protective cover member 1 is arranged on a surface 53 of an object 51 having a surface 53 with an opening 52. The protective cover member 1 is fixed to the surface 53 via an adhesive layer 3. In this example, the adhesive layer 3 (cured adhesive layer 11) constitutes a bonding surface 12 with the surface 53 of the object 51.

[0059] The adhesive layer 3 may have a laminated structure as long as it includes the cured adhesive layer 11 . The laminated structure may include two or more adhesive layers, and at least one adhesive layer or all adhesive layers selected from the two or more adhesive layers may be the cured adhesive layer 11 .

[0060] The adhesive layer 3 may include an adhesive tape comprising a substrate and a cured adhesive layer 11 disposed on at least one surface of the substrate. The adhesive tape may be a double-sided adhesive tape. An example of this method is shown in Figure 3 . Figure 3 The adhesive layer 3 is a double-sided adhesive tape 14 having a substrate 13A and adhesive layers 13B provided on both sides of the substrate 13A. One adhesive layer 13B is in contact with the protective film 2. The other adhesive layer 13B constitutes the bonding surface 12 of the protective cover member 1. At least one of the two adhesive layers 13B is a cured adhesive layer 11, and both may be cured adhesive layers 11. The double-sided adhesive tape 14 may be a substrate-free tape without the substrate 13A.

[0061] Figure 4A and Figure 4BThe adhesive layer 3 is a laminated structure composed of a single-sided adhesive tape 15 having a substrate 13A and an adhesive layer 13B provided on one side of the substrate 13A and an adhesive layer 13C. Figure 4A In the adhesive layer 3 , the adhesive layer 13B of the single-sided adhesive tape 15 constitutes the bonding surface 12 , and the adhesive layer 13C is in contact with the protective film 2 . Figure 4B In the adhesive layer 3, the adhesive layer 13B of the single-sided adhesive tape 15 is in contact with the protective film 2, and the adhesive layer 13C constitutes the bonding surface 12. The adhesive layer 13B or the adhesive layer 13C is the cured adhesive layer 11, and both the adhesive layer 13B and the adhesive layer 13C may be the cured adhesive layer 11. In addition, the adhesive layer 13C may have the same structure as the adhesive layer 3 (including the mode having the above-mentioned laminated structure), or may be the above-mentioned double-sided adhesive tape 14.

[0062] Substrate 13A is, for example, a film, nonwoven fabric or foam of a resin, metal or a composite material thereof. Examples of resins are polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate (PET), silicone resins, polycarbonates, polyimides, polyamide-imides, polyphenylene sulfide, polyetheretherketone (PEEK), and fluororesins. Examples of fluororesins are polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers (PFA), tetrafluoroethylene-hexafluoropropylene copolymers (FEP), and tetrafluoroethylene-ethylene copolymers (ETFE). Examples of metals are stainless steel and aluminum. Among them, resins and metals are not limited to the above examples.

[0063] The substrate 13A may include a heat-resistant material. In this case, by utilizing the materials of the other layers constituting the protective cover member 1, a more reliable response to use at high temperatures can be achieved. Examples of heat-resistant materials are metals and heat-resistant resins. Heat-resistant resins typically have a melting point of 150°C or more. The melting point of the heat-resistant resin may be above 160°C, above 200°C, above 250°C, above 260°C, and further above 300°C. Examples of heat-resistant resins are silicone resins, polyimides, polyamide-imides, polyphenylene sulfide, PEEK, and fluororesins. The fluororesin may be PTFE. PTFE is particularly excellent in heat resistance.

[0064] Figure 1B The adhesive layer 3 is disposed on a partial region of the protective film 2 when viewed from a direction perpendicular to the main surface of the protective film 2 . Figure 1B The shape of the adhesive layer 3 is the shape of the peripheral portion of the protective film 2 when viewed from a main surface perpendicular to the protective film 2, more specifically, a frame shape. In this case, the region P of the protective film 2 where the adhesive layer 3 is not formed can achieve good air permeability and / or sound permeability compared to the region where the adhesive layer 3 is formed. However, the shape of the adhesive layer 3 is not limited to the above example.

[0065] The area of ​​the region P of the protective film 2 is, for example, 20 mm 2 The protective cover member 1 having the area of ​​the region P within this range is suitable for placement on, for example, a circuit board or MEMS that generally has a small-diameter opening. The lower limit of the area of ​​the region P is, for example, 0.008 mm 2 However, the area of ​​the region P may be a larger range depending on the type of the object on which the protective cover member 1 is placed.

[0066] The thickness of the adhesive layer 3 is, for example, 10 to 200 μm.

[0067] The protective film 2 may be non-permeable in the thickness direction or may have permeability in the thickness direction. When the protective film 2 has permeability in the thickness direction, the configuration of the protective cover member 1 can, for example, prevent the intrusion of foreign matter through the opening of the object and ensure the permeability of the above-mentioned opening. By ensuring permeability, for example, it is possible to adjust the pressure by means of the opening of the object and to ease the pressure fluctuation. An example of easing the pressure fluctuation is shown below. Sometimes, a heating treatment such as reflow soldering is performed in a state where a semiconductor element is configured in a manner covering an opening of a through hole provided in a circuit substrate. Here, by configuring the protective cover member 1 in a manner covering the opening on the other side, it is possible to suppress the intrusion of foreign matter into the element through the through hole during the heating treatment. If the protective film 2 has permeability in the thickness direction, the pressure rise in the through hole caused by heating is eased, thereby preventing damage to the element caused by the pressure rise. Examples of semiconductor elements are MEMS such as microphones, pressure sensors, and acceleration sensors. These elements have an opening that is permeable to air or sound, and the opening can be configured on the circuit substrate in a manner facing the above-mentioned through hole. The protective cover member 1 can be arranged on the element in a manner to cover the opening of the manufactured semiconductor element. When the protective film 2 has air permeability in the thickness direction, the arranged protective cover member 1 can, for example, function as a breathable member that prevents foreign matter from invading through the opening of the object and ensures air permeability through the opening, and / or a sound-permeable member that prevents foreign matter from invading through the opening of the object and ensures sound permeability through the opening. It should be noted that even when the protective film 2 is non-air-permeable in the thickness direction, the transmission of sound caused by the vibration of the protective film 2 can be achieved, so the arranged protective cover member 1 can function as a sound-permeable member.

[0068] The air permeability of the protective film 2 having air permeability in the thickness direction is represented by air permeability (Gurley air permeability) determined by air permeability measurement method B (Gurley method) specified in JIS L 1096, and is, for example, 100 sec / 100 mL or less.

[0069] The protective film 2 may be waterproof. The protective cover member 1 having the waterproof protective film 2 can function as, for example, a waterproof air-permeable member and / or a waterproof sound-permeable member after being arranged on an object. The water pressure resistance of the waterproof protective film 2 is a value obtained by the water resistance test method A (low water pressure method) or method B (high water pressure method) specified in JIS L1092, for example, 5 kPa or more.

[0070] Examples of the material constituting the protective film 2 include metals, resins, and composite materials thereof.

[0071] Examples of the resin and metal that can constitute the protective film 2 are the same as the examples of the resin and metal that can constitute the base material 13A. However, the resin and metal are not limited to the above examples.

[0072] The protective film 2 may be made of a heat-resistant material. In this case, by using the materials of the other layers constituting the protective cover member 1, it is possible to achieve more reliable response to high-temperature processing such as reflow soldering. Examples of heat-resistant materials are described in the description of the substrate 13A. As an example, the protective film 2 may include a PTFE film.

[0073] The protective film 2 with air permeability in the thickness direction can include a stretched porous film. The stretched porous film can be a stretched porous film of a fluororesin, particularly a PTFE stretched porous film. The PTFE stretched porous film is usually formed by stretching a paste extrudate or a cast film containing PTFE particles. The PTFE stretched porous film is composed of fine fibrils of PTFE, and sometimes has nodes in a state of PTFE aggregation compared to the fibrils. Utilizing the PTFE stretched porous film, it is possible to take into account both the performance and air permeability of preventing foreign matter from intruding at a high level. The protective film 2 can use a known stretched porous film.

[0074] Therefore, when the protective film 2 includes a stretched porous film, especially when the cured adhesive layer 11 is in contact with the protective film 2, the effect of the present invention of suppressing deformation of the protective cover member 1 and peeling from the configuration surface even at high temperatures becomes more advantageous.

[0075] The protective film 2 with air permeability 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 an original film having a non-porous matrix structure, for example, a film having a plurality of through holes provided in a non-porous film. The perforated film may not have an air permeability path in the thickness direction except for the above-mentioned plurality of through holes. The through holes may be along the thickness direction of the perforated film, or may be straight holes extending in a straight line in the thickness direction. The shape of the opening of the through hole may be a circle or an ellipse when observed perpendicular to the main surface of the perforated film. The perforated film may be formed, for example, by laser processing of the original film, or by hole-opening processing based on ion beam irradiation and subsequent chemical etching.

[0076] The protective film 2 having air permeability in the thickness direction may be made of nonwoven fabric, woven fabric, mesh, or net.

[0077] The protective film 2 is not limited to the above-mentioned example.

[0078] Figure 1B The shape of the protective film 2 is a rectangle when viewed perpendicularly to its main surface. However, the shape of the protective film 2 is not limited to the above example. For example, the shape of the protective film 2 may be a polygon including a square and a rectangle, a circle, or an ellipse when viewed perpendicularly to its main surface. The polygon may be a regular polygon. The corners of the polygon may be rounded.

[0079] The thickness of the protective film 2 is, for example, 1 to 100 μm.

[0080] The area of ​​the protective film 2 is, for example, 175 mm 2 Below, can be 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, and further 7.5mm 2 The protective cover member 1 having the area of ​​the protective film 2 within the above range is suitable for placement on, for example, a circuit board or MEMS which generally has a small opening. The lower limit of the area of ​​the protective film 2 is, for example, 0.20 mm 2 However, the area of ​​the protective film 2 may be larger depending on the type of the object on which the protective cover member 1 is placed.

[0081] Figure 1B The adhesive layer 3 is arranged at the peripheral portion of the protective film 2 when viewed perpendicularly to the main surface of the protective film 2. At this time, when viewed perpendicularly to the main surface of the protective film 2, the shortest line segment S between the center O of the protective film 2 and the outer periphery of the protective film 2 is min The length L2 of the portion overlapping with the adhesive layer 3 is relative to the line segment S minThe ratio L2 / L1 of the length L1 can be less than 0.5, or less than 0.3, less than 0.2, or less than 0.1. The lower limit of the ratio L2 / L1 is, for example, greater than 0.05. The smaller the ratio L2 / L1, the greater the impact of the shrinkage of the adhesive layer 3 on the protective cover component 1, and in particular, it becomes easier to cause the protective film 2 and / or the configuration surface to peel off from the adhesive layer 3. Therefore, when the ratio L2 / L1 is within the above range, the effect of the present invention becomes more favorable. It should be noted that the center O of the protective film 2 can be defined as the center of gravity of the shape of the protective film 2 when observed from the main surface perpendicular to the protective film 2.

[0082] The laminate 4 may include: a first adhesive layer located on one main surface side of the protective film 2, and a second adhesive layer located on the other main surface side of the protective film 2. In this case, for example, by using one adhesive layer selected from the first adhesive layer and the second adhesive layer, it is possible to achieve configuration on the surface of the object, and it is possible to configure a further layer on the other adhesive layer, or to bond the other adhesive layer to any member and / or surface, etc. At least one adhesive layer selected from the first adhesive layer and the second adhesive layer may be an adhesive layer 3 having a cured adhesive layer 11. It may also be possible as Figure 5 As shown, both the first adhesive layer located on one main surface 16A side of the protective film 2 and the second adhesive layer located on the other main surface 16B side are adhesive layers 3 (3A, 3B) having a cured adhesive layer 11. When both are adhesive layers 3, deformation of the protective cover member 1 at high temperatures and suppression of peeling from the configuration surface are more reliably prevented.

[0083] Figure 5 The shape of the adhesive layer 3B is the same as the shape of the adhesive layer 3A when observed perpendicularly to the main surface of the protective film 2. In this case, the region Q of the protective film 2 where the adhesive layer 3B is not formed can achieve good air permeability and / or sound permeability compared to the region where the adhesive layer 3B is formed. Among them, the shape of the adhesive layer 3B is not limited to the above example. The shape of the adhesive layer 3B may be different from the shape of the adhesive layer 3A when observed perpendicularly to the main surface of the protective film 2. The area of ​​the region Q can be set to the same range as the area of ​​the region P. The area of ​​the region Q may be the same as the area of ​​the region P.

[0084] 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 the protective cover member 1 including further layers is shown in FIG. Figure 6 .

[0085] Figure 6 The laminate 4 has a cover film 5 covering the protective film 2 on the other main surface 16B side (adhesive layer 3B side) of the protective film 2. Figure 5The cover film 5 is arranged on the adhesive layer 3B. Other layers may be arranged between the adhesive layer 3B and the cover film 5. The cover film 5 functions as a protective film for protecting the protective film 2, for example, until the protective cover member 1 is arranged on the object. The cover film 5 can be peeled off after the protective cover member 1 is arranged on the object. The cover film 5 may cover the entire protective film 2 or a part thereof when viewed perpendicularly to the main surface of the protective film 2.

[0086] Figure 6 The cover film 5 has a tab 6 which is a portion protruding outward from the outer periphery of the protective film 2 when viewed perpendicularly to the main surface of the protective film 2. The tab 6 can be used to peel off the cover film 5. However, the shape of the cover film 5 is not limited to the above example.

[0087] Examples of the material constituting the cover film 5 include metal, resin, and composite materials thereof. Specific examples of the material that can constitute the cover film 5 are the same as the specific examples of the material that can constitute the base material 13A.

[0088] The thickness of the cover film 5 is, for example, 200 to 1000 μm.

[0089] Figure 1A and Figure 1B The shape of the protective cover member 1 is a rectangle when viewed perpendicularly 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 perpendicularly to the main surface of the protective film 2. The polygon may be a regular polygon. The corners of the polygon may be rounded.

[0090] The area of ​​the protective cover member 1 (the area when viewed perpendicularly to the main surface of the protective film 2) is, for example, 175 mm 2 Below, can be 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, and further 7.5mm 2 The protective cover member 1 having an area within the above range is suitable for placement on, for example, a circuit board or MEMS that generally has a small-diameter opening. The lower limit of the area of ​​the protective cover member 1 is, for example, 0.20 mm 2However, the area of ​​the protective cover member 1 can be a larger value depending on the type of the object to be configured. It should be noted that the smaller the area of ​​the protective cover member 1, the easier it is to deform at high temperature and peel off from the configuration surface. Therefore, when the area of ​​the protective cover member 1 is within the above range, the effect of the present invention becomes particularly advantageous.

[0091] Examples of objects to which the protective cover member 1 is configured are semiconductor elements such as MEMS, and circuit substrates. In other words, the protective cover member 1 can be a member for semiconductor elements, circuit substrates, or MEMS with semiconductor elements, circuit substrates, or MEMS as the object. MEMS can be a non-sealed element having air holes on the surface of the package. Examples of non-sealed MEMS are various sensors for detecting air pressure, humidity, gas, airflow, and electroacoustic conversion elements such as speakers and microphones. In addition, the object is not limited to the semiconductor element and circuit substrate after manufacture, but can be an intermediate product of these elements and substrates in the manufacturing process. In this case, the protective cover member 1 can be used to protect the intermediate product in the manufacturing process. Examples of manufacturing processes are reflow soldering process, cutting process, bonding process, and installation process. For the manufacturing process, the reflow soldering process can be the first, and it can be a process implemented at high temperature. The high temperature is, for example, above 200°C, and can be above 220°C, above 240°C, and further above 260°C. The reflow soldering process is usually implemented at about 260°C. However, the object is not limited to the above examples.

[0092] The surface of the object on which the protective cover member 1 can be disposed is typically the outer surface of the object. The surface may also be the internal surface of the object. The surface may be a flat surface or a curved surface. In addition, the opening of the object may be the opening of a recess or the opening of a through hole.

[0093] The protective cover member 1 can be produced, for example, by laminating the protective film 2 and the adhesive layer 3 .

[0094] [Component supply sheet]

[0095] Figure 7 An example of the member supplying sheet of the present invention is shown in FIG. Figure 7 The component supply sheet 21 includes a base sheet 22 and a plurality of protective cover members 1 arranged on the base sheet 22. The component supply sheet 21 is a sheet for supplying the protective cover members 1. The component supply sheet 21 can efficiently supply the protective cover members 1 to a process of being arranged on a surface of an object, for example.

[0096] Figure 7 In the example of FIG. 2 , two or more protective cover members 1 are arranged on the base sheet 22. The number of protective cover members 1 arranged on the base sheet 22 may be one.

[0097] Figure 7 In the example, more than two protective cover members 1 are regularly arranged on the substrate sheet 22. More specifically, the protective cover members 1 are arranged in such a manner that the center of each protective cover member 1 is located at the intersection point (lattice point) of the rectangular lattice when observed perpendicularly to the surface of the substrate sheet 22. However, the arrangement of the regularly arranged protective cover members 1 is not limited to the above example. They can also be regularly arranged in such a manner that the center of each protective cover member 1 is located at the intersection point of various lattices such as a square lattice, a rhombus lattice, and a diamond lattice. In addition, the arrangement of the protective cover members 1 is not limited to the above example. For example, when observed perpendicularly to the surface of the substrate sheet 22, the protective cover members 1 are arranged in a zigzag shape. It should be noted that the center of the protective cover member 1 can be defined as the center of gravity of the shape of the member 1 when observed perpendicularly to the surface of the substrate sheet 22.

[0098] Examples of materials constituting the substrate sheet 22 include paper, metal, resin, and composite materials thereof. Examples of metals include stainless steel and aluminum. Examples of resins include polyesters such as PET, and polyolefins such as polyethylene and polypropylene. However, the materials constituting the substrate sheet 22 are not limited to the above examples.

[0099] The protective cover member 1 can be arranged on the base sheet 22 via the adhesive layer (e.g., adhesive layer 3) provided in the member 1. At this time, the surface of the base sheet 22 where the protective cover member 1 is arranged can be subjected to a release treatment to improve the releasability from the base sheet 22. The release treatment can be performed by a known method.

[0100] The protective cover member 1 can be arranged on the base sheet 22 via an adhesive layer, typically a weak adhesive layer, provided on the surface of the base sheet 22 where the protective cover member 1 is arranged.

[0101] The thickness of the base sheet 22 is, for example, 1 to 200 μm.

[0102] Figure 7 The substrate sheet 22 is a single sheet having a rectangular shape. The shape of the single sheet substrate sheet 22 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 substrate sheet 22 is a single sheet, the component supply sheet 21 can be circulated and used in a single sheet state. The substrate sheet 22 may be a strip-shaped sheet, in which case the component supply sheet 21 is also a strip-shaped sheet. The strip-shaped component supply sheet 21 can be circulated in the form of a winding body wound around a winding core.

[0103] The member supply sheet 21 can be manufactured by placing the protective cover member 1 on the surface of the base sheet 22 .

[0104] Example

[0105] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the examples shown below.

[0106] First, the evaluation method of the cured adhesive layer (in Comparative Example 4, it is an acrylic adhesive layer. The same shall apply hereinafter) will be described.

[0107] [Gel fraction]

[0108] The gel fraction of the cured adhesive layer was determined by the above-mentioned method. The temperature of the measurement environment was set to 25° C. and the humidity was set to 50% RH.

[0109] [Elastic modulus at 250°C]

[0110] The storage modulus (250°C) of the cured adhesive layer was determined by the above method. The rheometer used was Advanced Rheometric Expansion System (ARES) manufactured by Rheometric Scientific. The measurement sample was made circular, and the area in the plane direction was set to 78.5 mm. 2 , thickness is set to 5mm.

[0111] [Shrinkage at 260°C X]

[0112] The shrinkage X of the cured adhesive layer at 260°C is determined as follows. Sample B (a square with a side length of 1.7 mm having a three-layer structure of a cured adhesive layer / polyimide substrate (thickness 25 μm) / cured adhesive layer) prepared in each embodiment and comparative example is subjected to a heating treatment in a heating tank maintained at 260°C for 1 minute. After the treatment, the sample is cooled to 25°C, and the shortest dimension D of the cured adhesive layer is measured in the MD and TD directions of the cured adhesive layer. min The shortest dimension D of each of the two cured adhesive layers sandwiching the polyimide substrate is min The average value of is defined as the dimension D1 in each direction after the heat treatment. Based on the obtained D1, the shrinkage rate X (%) is calculated by the formula: shrinkage rate X = (1.7-D1) / 1.7×100 (%). The shortest dimension D min The shortest dimension D was obtained by analyzing the magnified image (magnification 47 times) observed using an optical microscope. min The measurement was carried out at a temperature of 25°C and a humidity of 50% RH.

[0113] [Adhesion to PTFE membrane]

[0114] The initial adhesive strength of the cured adhesive layer to the PTFE film and the adhesive strength after heat treatment (260° C., 1 minute) were determined by a 180° peel test as follows.

[0115] The sample A (a strip having a three-layer structure of a cured adhesive layer / polyimide substrate (thickness 25 μm) / cured adhesive layer, with a width of 20 mm and a length of 150 mm) prepared in each embodiment and comparative example is bonded to the surface of a rectangular fixed plate (stainless steel) having a length and width greater than that of the sample A and a sufficient thickness that will not deform during the test, by means of a cured adhesive layer. The bonding of the sample A is implemented in a manner that the long sides and short sides of both sides are parallel to each other. Next, a strip-shaped PTFE membrane (a strip having a thickness of 10 μm, a width of 50 mm and a length of 150 mm, an average pore size of less than 0.5 μm, and a porosity of 40%) is bonded to the sample A in a manner that the PTFE membrane is in contact with another cured adhesive layer. By using a microporous membrane with an average pore size of less than 0.5μm and a porosity of about 30-50%, the PTFE membrane will not aggregate and break even during a peel test. In addition, the contact state between the cured adhesive layer and the porous membrane can be properly ensured, thereby achieving appropriate measurement of the adhesion of the PTFE membrane. It should be noted that regarding the method for measuring the average pore size of the PTFE membrane, the method described in ASTM F316-86 is generally popular, and an automated measuring device (for example, a Perm Porometer available from Porous Materials Inc. in the United States) can be used for the measurement. The porosity of the PTFE membrane can be expressed by the formula: Porosity (%) = {1-(membrane mass [g] / (membrane thickness [cm] × membrane area [cm 2 ] × the true density of PTFE))} × 100. The true density of PTFE is 2.18 g / cm 2 .

[0116] The PTFE film used in the stripping test is made as follows. In a PTFE dispersion (40% by mass of PTFE powder, an average particle size of 0.2 μm of PTFE powder, a nonionic surfactant containing 6 parts by mass relative to 100 parts by mass of PTFE), 1 part by mass of a fluorine-based surfactant (DIC Co., Ltd., MEGAFACE F-142D) is added relative to 100 parts by mass of PTFE. Then, a long polyimide film (thickness 125 μm) is impregnated in the PTFE dispersion and lifted, and a coating film of the PTFE dispersion is formed on the film. At this time, a metering rod is utilized, and the thickness of the coating film is set to 20 μm. Then, the coating film is heated at 100 ° C for 1 minute, and then heated at 390 ° C for 1 minute, so that the water contained in the dispersion is evaporated and removed, and the remaining PTFE particles are bonded to each other. And then after repeating the above-mentioned dipping and heating twice, the original PTFE film (thickness 25 μm) formed is peeled off from the polyimide film. Next, the obtained PTFE original film was rolled in the MD direction at a rolling ratio of 2.5 times, and then stretched in the TD direction at a stretching ratio of 2.0 times using a tenter to obtain the above PTFE film. The rolling was performed using a roll rolling device, and the set temperature of the roll was set to 170°C. The stretching temperature was 170°C.

[0117] The lamination of sample A and PTFE film is implemented in a manner that the PTFE film covers the entirety of sample A and the long sides of the two are parallel to each other. Thereafter, a manual roller (a roller with a mass of 2 kg specified in JIS Z0237:2009) that presses the PTFE film, sample A and fixed plate is moved back and forth once with the fixed plate as the lower side. Next, one short side of the fixed plate is fixed to the upper chuck of the tensile test device, and the end of the upper chuck side of the PTFE film is peeled off from sample A, folded back 180°, fixed to the lower chuck of the tensile test device, and a 180° peeling test is performed to peel the PTFE film from sample A. The tensile speed is set to 300mm / minute. In order to ensure the measurement accuracy, after the test starts, the measured value of the initial 20mm length is ignored, and thereafter, the measured value of the adhesive force of at least 60mm peeled off from sample A is averaged and used as the adhesive force of the cured adhesive layer (unit: N / 20mm). The peeling test is implemented under an environment of temperature 25°C and humidity 50%RH. The above test was performed at various time points before and after the heat treatment to determine the adhesive strength before the heat treatment (initial adhesive strength) and the adhesive strength after the heat treatment. The heat treatment was performed by keeping Sample A in a heating bath maintained at 260° C. for 1 minute.

[0118] (Example 1)

[0119] As the addition reaction curing type silicone adhesive composition A, a mixture of 100 parts by weight of KR3700 manufactured by Shin-Etsu Chemical Co., Ltd. and 0.05 parts by weight of a platinum catalyst (manufactured by Shin-Etsu Chemical, CAT-PL-50T) (composition a) was prepared. KR3700 contains dimethyl polysiloxane as a main component A, MQ resin as a main component B, and hydrogen dimethyl polysiloxane as a main component C. In addition, KR3700 does not contain a peroxide curing type silicone adhesive.

[0120] Next, the two main surfaces of the polyimide substrate (a strip with a thickness of 25 μm, a width of 20 mm and a length of 150 mm) are coated with composition a in one direction, and the whole is heated at 130 ° C for 2 minutes, thereby curing the coating film of composition a to obtain a sample A with a three-layer structure of a cured adhesive layer / polyimide substrate / cured adhesive layer. The coating of composition a is implemented using an applicator in a manner that the thickness after curing becomes 30 μm. In addition, the coating direction of composition a is the same in the two main surfaces of the polyimide substrate. Sample B is obtained by cutting sample A into a square with a side length of 1.7 mm. The direction of each side of the square is set to the MD (coating direction of composition a) or TD (the direction orthogonal to MD in the surface of the cured adhesive layer) of the cured adhesive layer.

[0121] (Example 2)

[0122] Sample A (strip) and sample B (square) of Example 2 were obtained in the same manner as in Example 1 except that a mixture of 100 parts by weight of X-40-3240 manufactured by Shin-Etsu Chemical Co., Ltd. and 0.05 parts by weight of a platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) was used as the addition reaction curing type silicone adhesive composition A. X-40-3240 contains dimethyl polysiloxane as a main component A, MQ resin as a main component B, and hydrogen dimethyl polysiloxane as a main component C. In addition, X-40-3240 does not contain a peroxide curing type silicone adhesive.

[0123] (Example 3)

[0124] Sample A (strip) and sample B (square) of Example 3 were obtained in the same manner as in Example 1 except that a mixture of 75 parts by weight of KR3700 manufactured by Shin-Etsu Chemical Co., Ltd., 25 parts by weight of KR3704 manufactured by Shin-Etsu Chemical Co., Ltd., and 0.05 parts by weight of a platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) was used as the addition reaction curing type silicone adhesive composition A. KR3704 contains dimethyl polysiloxane as a main component A, MQ resin as a main component B, and hydrogen dimethyl polysiloxane as a main component C. In addition, KR3704 does not contain a peroxide curing type silicone adhesive.

[0125] (Example 4)

[0126] As the addition reaction curing type silicone adhesive composition A, a mixture of 25 parts by weight of KR3700 manufactured by Shin-Etsu Chemical Co., Ltd., 75 parts by weight of KR3704 manufactured by Shin-Etsu Chemical Co., Ltd., and 0.05 parts by weight of a platinum catalyst (manufactured by Shin-Etsu Chemical, CAT-PL-50T) was used. Except for this, the same operation as in Example 1 was carried out to obtain Sample A (strip) and Sample B (square) of Example 4.

[0127] (Comparative Example 1)

[0128] Sample A (strip) and sample B (square) of Comparative Example 1 were obtained in the same manner as in Example 1 except that a peroxide-curable silicone adhesive composition (SH4280 manufactured by Dow Corning Toray Co., Ltd. (1.2 parts by weight of peroxide compounding amount)) was used instead of the addition reaction-curable silicone adhesive composition A. The curing conditions of the coating film were set to 200° C. and 3 minutes.

[0129] (Comparative Example 2)

[0130] Sample A (strip) and sample B (square) of Comparative Example 2 were obtained in the same manner as in Example 1 except that a peroxide-curable silicone adhesive composition (SH4280 manufactured by Dow Corning Toray Co., Ltd. (the compounding amount of peroxide is 2.4 parts by weight)) was used instead of the addition reaction-curable silicone adhesive composition A. The curing conditions of the coating film were set to 200° C. and 3 minutes.

[0131] (Comparative Example 3)

[0132] Sample A (strip) and sample B (square) of Comparative Example 3 were obtained in the same manner as in Example 1 except that a peroxide-curable silicone adhesive composition (manufactured by Shin-Etsu Chemical Co., Ltd., KR101-10 (the amount of peroxide added: 2.4 parts by weight)) was used instead of the addition reaction-curable silicone adhesive composition A. The curing conditions of the coating film were set at 200° C. and 3 minutes.

[0133] (Comparative Example 4)

[0134] Sample A (strip) and sample B (square) of Comparative Example 4 were obtained in the same manner as in Example 1 except that an acrylic adhesive composition (manufactured by Nitto Denko, No. 5919) was used instead of the addition reaction curing type silicone adhesive composition A. However, instead of curing after coating, the coating film was dried by heating at 120° C. for 3 minutes. In addition, the adhesive composition was applied so that the thickness after drying was 50 μm.

[0135] The evaluation results are shown in the following Table 1A and Table 1B. In addition, the appearance of the sample B of each example and comparative example after the heat treatment (260°C, 1 minute) performed in the evaluation of the shrinkage rate X is shown in Figure 8 .

[0136] [Table 1A]

[0137]

[0138] [Table 1B]

[0139]

[0140] As shown in Table 1A and Table 1B, the shrinkage of the cured adhesive layer caused by the heat treatment in the examples was suppressed compared with the comparative examples. In addition, for Examples 1 to 3 in which the gel fraction was in the range of 25 to 65 wt %, the adhesive force to PTFE was improved compared with Example 4 in which the gel fraction was outside the above range, and the adhesive force after the heat treatment was also improved compared with the initial adhesive force. It should be noted that Figure 8 As shown, peeling 61 occurred from the cured adhesive layer of the polyimide substrate in Comparative Example 1. The peeling 61 progressed from the outer periphery of the sample B to the portion indicated by reference numeral 62 .

[0141] Industrial Applicability

[0142] The protective cover member of the present invention can be used, for example, for the production of semiconductor elements such as MEMS and / or circuit boards including the elements.

Claims

1. A protective cover member, arranged on a surface of an object having a surface with an opening, The protective cover member is composed of a laminated body including a protective film and an adhesive layer, wherein the protective film has a shape covering the opening when the member is arranged on the surface. The adhesive layer comprises a cured adhesive layer of a silicone adhesive composition containing an addition reaction curable silicone adhesive, and the gel fraction of the cured adhesive layer is 25 to 65% by weight. The organic silicon adhesive composition comprises an organic silicon compound having an addition reaction group, an organic silicon resin, a hydrosilane compound and a catalyst. The organosilicon compound having an addition reaction group is at least one of an organopolysiloxane having an addition reaction group and a partial condensate thereof, The organic silicone resin is at least one of an organic polysiloxane and a partial condensate thereof having a Q unit and at least one unit selected from an M unit, a D unit and a T unit, wherein the M unit is composed of R3SiO 1 / 2 The D unit is represented by R2SiO, and the T unit is represented by RSiO 3 / 2 It indicates that, R is independently a hydrocarbon group having 1 to 8 carbon atoms, The hydrosilane compound is a component having a Si—H group and reacting with an addition reaction group of an organic silicon compound having an addition reaction group to form a crosslinking structure.

2. The protective cover member according to claim 1, wherein: The silicone adhesive composition includes the addition reaction curable silicone adhesive as a main component.

3. The protective cover member according to claim 1, wherein: The silicone adhesive composition does not contain a peroxide-curable silicone adhesive.

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

5. The protective cover member according to claim 1, wherein The adhesive layer and / or the cured adhesive layer serves as a bonding surface with the surface of the object.

6. The protective cover member according to claim 1, wherein: The laminate includes the first adhesive layer located on one main surface side of the protective film and the second adhesive layer located on the other main surface side of the protective film.

7. The protective cover member according to claim 1, wherein: The adhesive layer includes an adhesive tape including a substrate and the cured adhesive layer disposed on at least one surface of the substrate.

8. The protective cover member according to claim 7, wherein: The adhesive tape is a double-sided adhesive tape.

9. The protective cover member according to claim 7, wherein: The substrate includes a heat-resistant resin.

10. The protective cover member according to claim 1, wherein The protective film has air permeability in the thickness direction.

11. The protective cover member according to claim 1, wherein: The protective film includes a polytetrafluoroethylene film.

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

13. The protective cover member according to claim 1, wherein: When viewed perpendicularly to the main surface of the protective film, The adhesive layer is arranged on the peripheral edge of the protective film. A ratio L2 / L1 of a length L2 of a portion overlapping with the adhesive layer in the shortest line segment among line segments from the center of the protective film to the periphery of the protective film to a length L1 of the shortest line segment is 0.3 or less.

14. The protective cover member according to claim 1, which is used in a micro-electro-mechanical system (MEMS).

15. A member supplying sheet comprising: a base sheet, and one or more protective cover members arranged on the base sheet, The protective cover member is the protective cover member according to any one of claims 1 to 14.

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