阅读说明：本技术 防水罩 (Waterproof cover ) 是由 福岛玉青 菅谷阳辅 北川寿惠 于 2020-04-16 设计创作，主要内容包括：提供一种防水罩,其具备：防水膜、和层叠于上述防水膜的外周边缘部的粘合片。上述粘合片包含接合于上述防水膜的粘合剂层。构成上述粘合剂层的粘合剂在40℃的储能模量G’为53000Pa以上。(Provided is a waterproof cover which is provided with: a waterproof film and an adhesive sheet laminated on the peripheral edge of the waterproof film. The adhesive sheet includes an adhesive layer bonded to the waterproof film. The adhesive constituting the adhesive layer has a storage modulus G' at 40 ℃ of 53000Pa or more.)

1. A waterproof cover is provided with:

a water-repellent film, and

an adhesive sheet laminated on the outer peripheral edge portion of the waterproof film,

the adhesive sheet comprises an adhesive layer bonded to the waterproofing membrane,

the adhesive constituting the adhesive layer has a storage modulus G' at 40 ℃ of 53000Pa or more.

2. The waterproof cover according to claim 1, wherein said adhesive is cross-linked with an epoxy-based cross-linking agent.

3. The waterproof cover according to claim 1 or 2, wherein the adhesive has a gel fraction of 35% or more.

4. The waterproof cover according to any one of claims 1 to 3, wherein said adhesive is an acrylic adhesive based on an acrylic polymer.

5. The waterproof cover according to any one of claims 1 to 4, wherein said adhesive comprises a tackifier.

6. The waterproof cover according to any one of claims 1 to 5, wherein the offset distance in a holding force test at 80 ℃ of the adhesive sheet is 0.4 mm/hr or less.

7. The waterproof cover according to any one of claims 1 to 6, wherein the adhesive sheet is a double-sided adhesive sheet with a substrate, and the adhesive sheet has: the adhesive sheet comprises a base material having a first surface and a second surface, the adhesive layer being an inner adhesive disposed on the first surface, and an outer adhesive layer disposed on the second surface.

8. The waterproof cover according to claim 7, wherein the substrate is a resin film.

9. A waterproof case is provided with:

a container having an opening, and

the waterproof cover according to any one of claims 1 to 8 attached to the container so as to close the opening.

10. An electronic device is provided with:

a container with an opening,

An electronic component accommodated in the container, and

the waterproof cover according to any one of claims 1 to 8 attached to the container so as to close the opening.

Technical Field

The present invention relates to a waterproof cover.

The present application claims priority based on japanese patent application No. 2019-079643, filed on 18/4/2019, the entire contents of which are incorporated by reference in the present specification.

Background

A waterproof film is sometimes applied to a case for housing articles such as electronic components and precision instruments which are hydrophobic. For example, in a case of an electronic device having a voice function such as a smart phone or a game device, an opening is usually provided at a position corresponding to a sound emitting unit and a sound receiving unit such as a speaker, a microphone, or a buzzer. In order to prevent foreign matter such as water droplets and dust from entering the opening into the housing, a waterproof film (waterproof sound-transmitting film) having both sound transmission performance (sound transmission performance) and waterproof performance is often disposed in the opening. Further, a case housing a component that generates heat such as a lamp for a vehicle or the like, a case of a home electric appliance, or the like is often provided with an opening for ensuring air permeability (typically, air circulation) between the outside and the inside of the case. Thereby, for example, a pressure difference that may be generated between the inside and the outside of the housing can be eliminated or reduced. In order to ensure air permeability and prevent water from entering the interior of the housing through the opening, a waterproof film (waterproof breathable film) having both air permeability and waterproof property is often disposed in the opening. Patent documents 1 and 2 are cited as technical documents relating to a waterproof film.

Documents of the prior art

Patent document

Patent document 1: japanese patent application laid-open No. 2014-31412

Patent document 2: japanese patent application laid-open No. 2003-128831

Disclosure of Invention

Problems to be solved by the invention

The waterproof film is typically disposed in the opening of the case by fixing the peripheral edge portion of the waterproof film to the periphery of the opening. For example, a method of manufacturing a waterproof cover in which an adhesive sheet is laminated on the outer peripheral edge portion of a waterproof film in advance and fixing the waterproof cover around the opening may be employed. The waterproof cover is easy to handle because the peripheral edge part of the waterproof membrane is reinforced by the adhesive sheet.

The waterproof membrane disposed in the opening of the case is preferably free from wrinkles in a portion to cover the opening, from the viewpoints of improvement in appearance quality, improvement in sealing properties, prevention or suppression of deterioration or change in acoustic characteristics, and the like. However, the present inventors have found that, in a waterproof cover in which an adhesive sheet is laminated on the outer peripheral edge portion of a waterproof film, even if wrinkles do not occur in the waterproof film at the time of first manufacturing the waterproof cover or at the time of first arranging the waterproof film on a housing, the waterproof film is observed to be wrinkled over time.

Accordingly, an object of the present invention is to provide a waterproof cover in which wrinkles of a waterproof film due to the passage of time are less likely to occur. Another related object is to provide a waterproof case provided with such a waterproof cover and an electronic device provided with the waterproof case.

Means for solving the problems

According to the specification, there is provided a waterproof cover including: a waterproof film and an adhesive sheet laminated on the peripheral edge of the waterproof film. The adhesive sheet includes an adhesive layer bonded to the waterproof film. The adhesive constituting the adhesive layer has a storage modulus G '(hereinafter, also referred to as "storage modulus G' at 40 ℃) of 53000Pa or more at 40 ℃. With the waterproof cover having the above configuration, it is possible to suppress positional deviation of the waterproof film with respect to the adhesive sheet (for example, positional deviation with unevenness such as anisotropic shrinkage), and to prevent the occurrence of wrinkles in the waterproof film due to the passage of time.

In some embodiments of the waterproof cover disclosed herein, the adhesive is preferably crosslinked with an epoxy-based crosslinking agent. The adhesive crosslinked with the epoxy crosslinking agent tends to effectively suppress the occurrence of wrinkles in the waterproof film over time.

In some embodiments, the gel fraction of the pressure-sensitive adhesive is preferably 35% or more. The adhesive having a gel fraction of 35% or more tends to effectively suppress the occurrence of wrinkles in the waterproof film over time.

In some embodiments, an acrylic adhesive containing an acrylic polymer as a base polymer can be preferably used as the adhesive. The waterproof sheet disclosed herein can be preferably implemented in a manner that the adhesive sheet is bonded to the waterproof film with an acrylic adhesive.

In some embodiments, the adhesive may comprise a tackifier. By using the tackifier, the adhesiveness to the waterproof film is improved, and the positional deviation of the waterproof film with respect to the adhesive sheet can be more favorably suppressed. This makes it possible to effectively suppress the occurrence of wrinkles in the waterproof film due to the passage of time.

In some embodiments, the adhesive sheet preferably has a displacement distance of 0.4 mm/hr or less in a holding power test at 80 ℃. The pressure-sensitive adhesive sheet exhibiting such a holding property has a high effect of suppressing the positional deviation of the waterproof film, and is suitable for preventing the occurrence of wrinkles caused by the passage of time.

In a preferred aspect of the waterproof cover, the adhesive sheet is a double-sided adhesive sheet, that is, a double-sided adhesive sheet in which both the first surface and the second surface of the adhesive sheet have adhesiveness. According to the waterproof cover in which the double-sided adhesive sheet is laminated on the outer peripheral edge portion of at least one surface of the waterproof film, the waterproof cover can be attached to the adherend with good workability by utilizing the adhesiveness of the double-sided adhesive sheet to the surface (outer adhesive surface) on the opposite side to the side bonded to the waterproof film.

In some embodiments, the double-sided pressure-sensitive adhesive sheet may preferably be a substrate-attached double-sided pressure-sensitive adhesive sheet including: the pressure-sensitive adhesive sheet includes a base having a first surface and a second surface, the pressure-sensitive adhesive layer being an inner pressure-sensitive adhesive layer disposed on the first surface, and an outer pressure-sensitive adhesive layer disposed on the second surface. The method using the double-sided adhesive sheet with a substrate is advantageous in view of strength, shape retention property, workability, and the like of the waterproof cover. As the substrate, a resin film can be preferably used.

In another embodiment, a substrate-less pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer may be preferably used as the double-sided pressure-sensitive adhesive sheet. The mode using the substrate-less pressure-sensitive adhesive sheet as described above is advantageous from the viewpoint of thinning, flexibility, workability, and the like of the waterproof cover.

According to the specification, there is provided a waterproof case including: a container having an opening, and a waterproof cover attached to the container so as to close the opening. As the waterproof cover, any of the waterproof covers disclosed herein may be used. This makes it easy to obtain a waterproof case without wrinkles in the waterproof film covering the opening. The waterproof case is preferable from the viewpoint of appearance, sealing property, performance stability, and the like because the waterproof film covering the opening is easily prevented from being wrinkled with time.

Such a waterproof case can be preferably used for the purpose of housing articles such as electronic components which are resistant to water. Therefore, according to the present specification, there is provided an electronic device including: the electronic component includes a container having an opening, an electronic component housed in the container, and a waterproof cover attached to the container so as to close the opening. As the waterproof cover, any of the waterproof covers disclosed herein may be used. The electronic device is preferable from the viewpoint of appearance, sealing property, performance stability, and the like because wrinkles are easily prevented from being generated in the waterproof film covering the opening with the passage of time.

The waterproof case described above can be preferably used for applications requiring waterproofness between the inside and outside of the case as well as sound permeability and/or air permeability. As one suitable example of such an application, an application of housing an acoustic component is cited. That is, the waterproof case disclosed herein can be preferably used as a waterproof case for housing audio components. In addition, according to the specification, there can be provided an acoustic apparatus including: any waterproof case disclosed herein and an audio component housed in the waterproof case.

Drawings

Fig. 1 is a perspective view schematically showing a waterproof cover according to an embodiment.

FIG. 2 is a sectional view taken along line II-II of FIG. 1.

Fig. 3 is a sectional view schematically showing another embodiment of a waterproof cover.

Fig. 4 is a front view schematically showing a smartphone having a case (waterproof case) mounted with a waterproof cover.

Fig. 5 is a sectional view schematically showing the structure of a waterproof cover sample for evaluation.

Detailed Description

Hereinafter, preferred embodiments of the present invention will be described. Matters necessary for carrying out the present invention other than the matters specifically mentioned in the present specification can be understood by those skilled in the art based on the teaching of the practice of the invention described in the present specification and the common general knowledge at the time of application. The present invention can be implemented based on the contents disclosed in the present specification and the common general knowledge in the art.

In the following drawings, members and portions that exhibit the same function are sometimes denoted by the same reference numerals, and redundant description may be omitted or simplified. The embodiments shown in the drawings are schematic for the purpose of clearly illustrating the present invention, and do not necessarily show actual dimensions or reduced dimensions accurately.

The "pressure-sensitive adhesive" in the present specification refers to a material that exhibits a soft solid (viscoelastic material) state in a temperature range around room temperature and has a property of easily adhering to an adherend by pressure. Also known as pressure sensitive adhesives. As used herein, an adhesive such as "c.a. dahlquist," bonding: basis and Practice ("Adhesion: Fundamental and Practice"), McLaren&Sons, (1966) P.143 ", as defined in, can generally have a modulus E satisfying the complex tensile elasticity^*(1Hz)<10⁷dyne/cm²A material having the above properties (typically, a material having the above properties at 25 ℃).

In this specification, the "base polymer" of the pressure-sensitive adhesive means a main component of a rubbery polymer (a polymer exhibiting rubber elasticity in a temperature range around room temperature) contained in the pressure-sensitive adhesive. In this specification, "main component" means a component having a content of more than 50% by weight unless otherwise specified.

In this specification, "(meth) acryloyl" refers inclusively to both acryloyl and methacryloyl. Likewise, "(meth) acrylate" inclusively refers to both acrylate and methacrylate, and "(meth) acrylic acid" inclusively refers to both acrylic acid and methacrylic acid.

The "acrylic polymer" in this specification means a polymer containing, as a monomer unit constituting the polymer, a monomer unit derived from a monomer having at least 1 (meth) acryloyl group in 1 molecule. Hereinafter, a monomer having at least 1 (meth) acryloyl group in 1 molecule is also referred to as an "acrylic monomer". Thus, an acrylic polymer in this specification is defined as a polymer comprising monomer units derived from an acrylic monomer. Typical examples of the acrylic polymer are polymers of monomer components containing more than 50% by weight of an acrylic monomer. In a preferred embodiment, the proportion of the acrylic monomer in the monomer component may be about 70% by weight or more (for example, about 90% by weight or more).

< structural example of waterproof cover >

Fig. 1 is a perspective view schematically showing a waterproof cover of an embodiment, and fig. 2 is a sectional view of line II-II thereof. The waterproof cover 10 of the present embodiment includes a waterproof film 12 and an adhesive sheet 14. The waterproof membrane 12 may be a membrane that functions as a waterproof sound-transmitting membrane and/or a waterproof breathable membrane. The waterproof cover 10 and the waterproof film 12 have a circular shape in a plan view. The adhesive sheet 14 has an annular (ring-like) shape in plan view, and is laminated on the outer peripheral edge portion of the one surface 12A of the waterproof film 12. The pressure-sensitive adhesive sheet 14 is a substrate-attached double-sided pressure-sensitive adhesive sheet including: a substrate 142, and a first adhesive layer (inner adhesive layer) 144 and a second adhesive layer (outer adhesive layer) 146 disposed on the first surface (waterproof film side surface) 142A and the second surface (outer surface) 142B. In this embodiment, the base 142, the first pressure-sensitive adhesive layer 144, and the second pressure-sensitive adhesive layer 146 have the same shape in a plan view. The adhesive sheet 14 is bonded to the waterproof film 12 with the first adhesive layer 144. The region inside the adhesive sheet 14 is an effective region of the waterproof membrane 12 (for example, a sound-transmitting region in the waterproof sound-transmitting membrane and a gas-permeable region in the waterproof gas-permeable membrane).

The waterproof cover 10 shown in fig. 1 can be fixed to an adherend by crimping the second adhesive layer 146 to the adherend. For example, by pressure-bonding the second pressure-sensitive adhesive layer 146 around the opening of a container (adherend) having an opening, a waterproof case in which the waterproof cover 10 is attached to the opening can be configured. In the embodiment shown in fig. 1, a double-sided adhesive sheet with a substrate is used as the adhesive sheet 14 bonded to the outer peripheral edge portion of the waterproof cover 10 with an adhesive layer, but the adhesive sheet 14 may be a substrate-free adhesive sheet formed of an adhesive layer (i.e., a substrate-free double-sided adhesive sheet). The waterproof cover of this embodiment can be attached to an adherend by, for example, pressing the surface on the opposite side of the pressure-sensitive adhesive layer bonded to the waterproof film against the adherend. Alternatively, the psa sheet 14 may be a substrate-attached one-sided psa sheet having the first psa layer 144 on the first side 142A of the substrate 142 and no psa layer on the second side 142B of the substrate 142. The waterproof cover of this embodiment can be attached to the adherend by, for example, adhesion with an adhesive such as an epoxy adhesive or an epoxy-modified polyimide adhesive, fusion bonding such as thermal fusion bonding or laser fusion bonding, or a mechanical method such as clamping or caulking.

Fig. 3 is a sectional view schematically showing another embodiment of a waterproof cover. The waterproof cover 20 of the present embodiment has substantially the same configuration as the waterproof cover 10 shown in fig. 1 except that it includes the adhesive sheet 14 laminated on the outer peripheral edge portion of the one surface 12A of the waterproof film 12 and the adhesive sheet 24 laminated on the outer peripheral edge portion of the other surface 12B of the waterproof film 12. The adhesive sheet 24 is a substrate-attached double-sided adhesive sheet including: a substrate 242, and a first adhesive layer 244 and a second adhesive layer 246 disposed on the first surface 242A and the second surface 242B. In this embodiment, the shapes of the substrate 242, the first pressure-sensitive adhesive layer 244, and the second pressure-sensitive adhesive layer 246 in a plan view are the same, and the shapes of the pressure-sensitive adhesive sheet 14 and the pressure-sensitive adhesive sheet 24 in a plan view are also the same. The adhesive sheet 24 is bonded to the waterproof film 12 with the first adhesive layer 244. The waterproof cover 20 shown in fig. 2 can be used by crimping the second adhesive layer 146 on one surface side of the waterproof film 12 to an adherend (for example, an inner wall around an opening of a container having the opening) and crimping the second adhesive layer 246 on the other surface side to another adherend (for example, a member constituting a sound emitting portion or a sound receiving portion such as a speaker or a microphone). The pressure-sensitive adhesive sheet 24 may be a substrate-free pressure-sensitive adhesive sheet or a substrate-attached single-sided pressure-sensitive adhesive sheet, as in the pressure-sensitive adhesive sheet 14.

The shape of the waterproof film included in the waterproof cover disclosed herein in a plan view is not limited to the circular shape as shown in fig. 1, and may be, for example, an elliptical shape, a rectangular shape, a polygonal shape other than a rectangular shape (for example, a triangular shape), or other irregular shapes. The pressure-sensitive adhesive sheet laminated on the outer peripheral edge portion of the waterproof film is typically in an annular (closed-loop) shape, but is not limited thereto, and may be, for example, an open-loop shape or a shape in which a loop is divided into a plurality of arcs.

In a preferred embodiment, the outer edge of the adhesive sheet in a plan view of the waterproof cover coincides with the outer edge of the waterproof film, for example, as in a waterproof cover 10 shown in fig. 1. Alternatively, a part or the whole of the outer edge of the adhesive sheet may be located inside or outside the outer edge of the waterproof film. For example, a part of the adhesive sheet may be formed into a tab (tab) in an outer direction from an outer edge of the waterproof film. In this case, as the pressure-sensitive adhesive sheet, a substrate-attached pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one side or both sides of a substrate (e.g., a resin film) can be preferably used from the viewpoint of strength and ease of formation of the sheet. The waterproof cover having the sheet formed on the adhesive sheet can be handled by gripping the sheet, and therefore, the waterproof cover is excellent in workability in mounting the waterproof cover to the case and the like. The pressure-sensitive adhesive sheet with a substrate may be configured so that the sheet portion does not have a pressure-sensitive adhesive layer on any surface of the substrate.

< Water-repellent film >

The waterproofing membrane used in the waterproof cover disclosed herein is not particularly limited. For example, various waterproofing membranes known to be useful as waterproof sound-transmitting membranes or waterproof breathable membranes can be employed as the waterproofing membrane of the waterproof cover disclosed herein.

In some embodiments, the water-repellent film may be made of a resin material selected from the group consisting of a fluorine-based resin such as Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene tetrafluoride hexafluoropropylene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), and ethylene chlorotrifluoroethylene copolymer (ECTFE), a polyester such as polyethylene terephthalate and polybutylene terephthalate, a polyolefin such as polycarbonate, polyethylene, and polypropylene, a polysulfone, a polyimide, a polyetherimide, and a polyamideimide; elastomers such as silicone rubber; and the like, or a film formed of two or more materials. The waterproof film may be a single-layer film or a laminated film in which a plurality of films are laminated.

As a suitable example of the waterproof film made of a resin material, a waterproof film made of PTFE is given. Such a waterproof film has a good balance between weight and strength, and is excellent in heat resistance. The waterproof film has heat resistance, and is advantageous when, for example, a waterproof cover is attached to an adherend (e.g., an acoustic component, a waterproof case usable in an electronic device, or the like) and then subjected to heat treatment (e.g., a reflow soldering step).

The waterproof film may be a non-porous film or a porous film. Here, "non-porous" means that there are no pores connecting one main surface of the film with the other main surface, or the number of pores is extremely small. For example, a membrane having an air permeability, as represented by a Gurley number, of greater than 1 ten thousand seconds per 100mL can be judged as a non-porous membrane.

When the waterproof film is a porous film, the air permeability of the waterproof film may be selected within a range that can obtain a desired waterproof property, and is not particularly limited. For example, a porous membrane having an air permeability in the range of 0.1 to 1 ten thousand seconds/100 mL can be preferably used as the waterproof membrane of the waterproof cover disclosed herein. The air permeability of the porous membrane may be, for example, 5000 seconds/100 mL or less, 1000 seconds/100 mL or less, or 300 seconds/100 mL or less. When a porous film having a smaller air permeability (Gurley number) is used, higher sound permeability is easily obtained. In some embodiments, the air permeability of the porous membrane may be 200 seconds/100 mL or less, or may be 100 seconds/100 mL or less. In some embodiments, the air permeability of the porous membrane may be, for example, 0.5 sec/100 mL or more, 1 sec/100 mL or more, or 5 sec/100 mL or more, from the viewpoint of strength and handling properties. The technique disclosed herein can also be preferably implemented using, as the waterproof membrane, a porous membrane having an air permeability of, for example, 10 seconds/100 mL or more, 20 seconds/100 mL or more, or 40 seconds/100 mL or more. In the present specification, the "Gurley number" refers to a value obtained by the B method (Gurley shape method) of the air permeability measurement method specified in Japanese Industrial Standard (JIS) L1096 (2010).

In the mode in which the waterproof film is a waterproof sound-transmitting film, sound can be transmitted by vibration of the waterproof film, and therefore it is not essential for the waterproof film to have air permeability. When the waterproof film is a non-porous film, there is an advantage that water vapor can be prevented from passing through the waterproof film and entering the inside of the case to which the waterproof film is attached. The water resistance of the nonporous film is generally superior to that of the porous film. On the other hand, the waterproof sound-transmitting membrane may be desired to have appropriate air permeability. For example, when the temperature inside the casing changes relatively greatly, appropriate air permeability can exert an effect of preventing dew condensation inside the casing. In this case, the waterproof film is preferably a porous film. The waterproof film which is porous and has air permeability can be also known as a waterproof breathable film.

In some embodiments, the thickness of the waterproof film formed of the resin material may be in a range of 1 μm or more and 25 μm or less, 1 μm or more and 20 μm or less, or 3 μm or more and 10 μm or less, for example. When the areal density and/or thickness are adjusted to an appropriate range, both the water resistance and the sound permeability of the waterproof film are easily achieved. The areal density is the weight of the film per unit area, and is calculated by dividing the weight of the film by the area of the film (the area of the main surface). The surface density of the waterproof film may be, for example, 1 to 30g/m²Can be in the range of 1 to 25g/m²Can be in the range of 5 to 20g/m²The range of (1).

When the waterproof film is formed of an elastomer, the elastomer can be selected from known rubber-like elastomers and thermoplastic elastomers. The rubber-like elastic body is not particularly limited as long as it is a material having rubber elasticity. Specific examples of the rubber-like elastic body include silicone rubber, ethylene-propylene-diene rubber (EPDM), acrylic rubber, urethane rubber, natural rubber, and the like. In particular, silicone rubber is preferably used from the viewpoint of heat resistance, chemical resistance, and the like. Examples of the thermoplastic elastomer include styrene-based, olefin-based, urethane-based, and ester-based thermoplastic elastomers. In order to achieve more excellent sound permeability, in some embodiments, a rubber-like elastic body (for example, silicone rubber) having a hardness in the range of 20 or more and 80 or less in type a according to JIS K6253 can be preferably used.

The thickness of the waterproof film made of an elastomer may be, for example, 10 μm or more and 150 μm or less. By setting the thickness in such a range, good sound permeability is easily obtained. In some embodiments, the thickness of the waterproof film may be 20 μm or more, or 30 μm or more, or 130 μm or less, or 110 μm or less. The waterproof film can be produced, for example, by the following method: a method of extruding a raw material solution into a thin layer on a releasable substrate by a discharging means such as a die; a method of casting the raw material solution on a releasable substrate and then forming a thin film by using an applicator, a wire bar, or a knife coater. Further, in these methods, the waterproof film may be adjusted to a desired thickness by cutting or the like.

When the water-repellent film is a porous film, the average pore diameter thereof is preferably in the range of, for example, 0.01 μm or more and 1 μm or less. The porosity of the waterproof film may be, for example, in the range of 5% to 95%, preferably 10% to 80%, and more preferably 20% to 50%. When the average pore diameter and/or the porosity is adjusted to an appropriate range, it is easy to achieve both the sound permeability and the water resistance of the waterproof membrane. The average pore diameter can be determined by a method according to ASTM (American society for testing and materials) F316-86. The porosity can be calculated by substituting the weight, volume, and true density of the waterproof film into the following equation. For example, when the material of the waterproof film is PTFE, 2.18g/cm is used as the value of the true density³。

Porosity (%) {1- (weight [ g) }]/(thickness [ cm)]X area [ cm ]²]X true density [ g/cm³]))}×100

The waterproof cover disclosed herein may include a breathable support material laminated on the waterproof film when the waterproof film is a porous film. The breathable support material has the function of supporting the waterproofing membrane. The breathable support material is effective to be laminated in a range including the inside of a region of the waterproof film where at least the adhesive sheet is laminated. The breathable support material may be laminated over the entire range of the waterproof film. The air-permeable support material may typically be a woven fabric, a nonwoven fabric, a mesh (mesh), a net (net), a sponge, a foam, or a porous body formed of a metal, a resin, or a composite material thereof. Examples of the resin include polyolefin, polyester, polyamide, polyimide, aramid, and fluororesin. Examples of the above polyolefins include ultra-high molecular weight polyethylene. The air-permeable support material may be laminated to the waterproof film by a method such as heat lamination, heat welding, ultrasonic welding, or bonding with an adhesive or bonding agent.

The water-repellent film may be subjected to coloring treatment. In other words, the water-repellent film may contain a colorant such as a pigment or a dye. Examples of the dye include azo dyes and oil-soluble dyes. As one example of a preferable colorant, carbon black is listed. For example, when carbon black is included, the waterproof film has a gray or black color tone. Here, "having a gray or black hue" means that a colorant for coloring to black is contained. In general, 1 to 4, 5 to 8, and 9 or more are judged as "black", gray ", and" white "respectively, by a jetness meter defined in JIS Z8721 (1993). The water-repellent film may be subjected to known treatments such as oil-repellent treatment and easy-adhesion treatment. These processes may be applied in combination as needed.

The oil-repellent treatment may be performed, for example, by applying an oil-repellent treatment agent solution to a water-repellent film and drying the film. The method of applying the oil repellent treatment agent solution is not particularly limited, and for example, a spray method, a spin coating method, a dip coating method, a roll coating method, or the like can be used. The oil-repellent treatment agent is not particularly limited, and a fluorine-based oil-repellent treatment agent is preferable. The fluorine-based oil repellent agent is preferably at least 1 kind selected from the group consisting of an acrylic polymer having a fluorine-containing side chain, a urethane polymer having a fluorine-containing side chain, and a silicone polymer having a fluorine-containing side chain, for example. As such a fluorine-based oil repellent treatment agent, commercially available products can be used. For example, DAIKIN INDUSTRIES, ltd, a series of "unityne (registered trademark)"; X-70-029C, X-70-043, made by shin-Etsu chemical Co., Ltd; AGC SEIMI CHEMICAL co, ltd, "SFCOAT (registered trademark)" series (e.g., SIF-200), and the like. Further, as a fluorine-based oil repellent treatment agent of the silicone polymer, there are, for example, KP-801M manufactured by shin-Etsu chemical Co.

An example of a method for producing a waterproof film made of PTFE will be described below.

First, a dispersion of PTFE powder (PTFE dispersion) is applied to a substrate to form a coating film. A colorant may be included in the dispersion. The substrate may be made of a heat-resistant material such as a heat-resistant plastic (polyimide, polyether ether ketone, or the like), a metal, or a ceramic. The shape of the substrate is not particularly limited, and may be, for example, a sheet, a tube or a rod. The dispersion can be applied to a substrate by a method of dipping the substrate in the dispersion and pulling it up, a method of spraying the dispersion onto the substrate, a method of brushing the dispersion on the substrate, or the like. In order to improve the wettability of the dispersion liquid with respect to the substrate surface, the dispersion liquid may contain a surfactant such as a silicone surfactant or a fluorine surfactant.

Subsequently, the coating film is heated. Thereby, the dispersion medium contained in the coating film is removed, and the PTFE particles are bonded to each other. After heating, a nonporous PTFE film is typically formed on one or both sides of the substrate. As a method of heating the coating film, for example, a two-stage heating method may be employed in which the coating film is heated at a temperature at which the dispersion medium can be evaporated in the 1 st stage to remove the dispersion medium, and then the coating film is heated (fired) at a temperature equal to or higher than the melting point of PTFE in the 2 nd stage to fuse PTFE particles. When the dispersion medium is water, the PTFE film can be formed on the substrate by heating the coating film at, for example, 90 to 150 ℃ in the 1 st stage and heating the coating film at, for example, 350 to 400 ℃ in the 2 nd stage. Alternatively, a one-stage heating method may be employed in which the coating film is heated at a temperature equal to or higher than the melting point of PTFE for a predetermined time.

Further, a PTFE film having a desired thickness can be formed by repeating the step of applying the dispersion to the substrate to form a coating film and the step of heating the coating film. The step of forming the coating film and the step of heating the coating film may be performed alternately, or the step of heating the coating film may be performed after repeating the step of forming the coating film, for example, 2 or more times.

Subsequently, the PTFE film (resin film) was peeled off from the substrate. Further, a step of rolling the PTFE film in the MD direction (longitudinal direction) and a step of stretching the PTFE film in the TD direction (width direction) are sequentially performed. Thereby, a waterproof film as a porous film was obtained. The step of stretching the PTFE film in the TD direction and the step of rolling the PTFE film in the MD direction may be performed in this order. When the rolling step is performed after the stretching step, the fine pores formed by stretching in the TD direction are crushed by rolling, and a waterproof film that is a non-porous film is obtained. Further, the PTFE membrane may be stretched in the MD direction during the formation of the nonporous membrane or porous membrane. Instead of the step of stretching the PTFE film in the TD direction, a step of rolling the PTFE film in the TD direction may be performed. The rolling magnification and the stretching magnification are appropriately set in consideration of the balance between the water repellency and the sound permeability in the waterproof sound-transmitting film, and the balance between the water repellency and the air permeability in the waterproof breathable film. The calendering magnification in the MD direction may be, for example, 1.25 to 3.5 times. The stretching ratio in the TD direction may be, for example, 1.25 to 3.5 times. The stretching magnification in the MD direction may be, for example, 1.25 to 3.5 times. The rolling magnification in the TD direction may be, for example, 1.25 to 3.5 times.

As a method for rolling the PTFE film, for example, a known method such as press rolling or roll rolling can be used. The pressure rolling is hot plate rolling in which a PTFE film is rolled while being heated by sandwiching the PTFE film between a pair of heating plates. Roll rolling is performed by, for example, passing a PTFE film between a pair of rolls (one or both of which are heated) to roll the PTFE film while heating it. Of the 2 rolling methods, roll rolling is more preferable because the orientation direction of PTFE is easily controlled and the tape-shaped PTFE film can be continuously rolled. The rolling may be carried out 2 or more times as necessary, and the rolling directions in this case may be the same or different.

The heating temperature for the pressing of the PTFE film may be, for example, 80 to 200 ℃. In the step of stretching the PTFE film, the PTFE film may be stretched while being heated. The heating temperature for stretching the PTFE film may be, for example, 100 to 400 ℃. The above temperature may be the ambient temperature of the PTFE film in the rolling device or stretching device. Alternatively, the stretching of the PTFE film may be performed at a temperature near room temperature (e.g., 10 to 60 ℃).

After the PTFE film is peeled from the substrate, a treatment for modifying at least a part of the surface of the PTFE film may be performed. By performing such a treatment, the adhesiveness of the waterproof film to another material (e.g., an adhesive) can be improved. The surface modification treatment (easy adhesion treatment) may be a PTFE modification treatment such as a chemical treatment or a sputter etching treatment. The surface modification treatment may be performed before the rolling step and the stretching step, or may be performed after these steps.

The chemical treatment is, for example, a treatment using an alkali metal such as sodium (alkali metal treatment). In the alkali metal treatment, for example, an etching solution containing sodium metal is brought into contact with the PTFE film, and fluorine atoms in a portion of the PTFE film in contact with the etching solution are abstracted to form a functional group, thereby improving adhesiveness. The PTFE film may be immersed in the etching solution so that the etching solution is in contact with the PTFE film. The etching liquid is, for example, a metal sodium/liquid ammonia solution in which metal sodium is dissolved in liquid ammonia, or a metal sodium/naphthalene solution in which metal sodium is dissolved in a naphthalene solution. Of these 2 solutions, the sodium metal/naphthalene solution is preferable in that the control and the treatment are easy and the treatment does not require a low temperature of about-50 ℃.

In the sputter etching process, energetic particles derived from a gas are made to impinge on the surface of the PTFE film. At the part of the PTFE film where the particles collide, atoms or molecules present on the surface of the PTFE film are releasedThereby forming a functional group, and thus improving adhesiveness. The sputter etching process can be performed, for example, by storing a PTFE film in a chamber, reducing the pressure in the chamber, and then applying a high-frequency voltage while introducing an atmospheric gas. The atmosphere gas is at least 1 kind selected from the group consisting of rare gases such as helium, neon, argon, krypton, nitrogen, and oxygen. The frequency of the applied high-frequency voltage is, for example, 1 to 100MHz, preferably 5 to 50 MHz. The pressure in the chamber when the high-frequency voltage is applied is, for example, 0.05 to 200Pa, preferably 1 to 100 Pa. The energy (product of the treatment time and the applied power) of the sputter etching is, for example, 1 to 1000J/cm²Preferably 2 to 200J/cm²。

< pressure-sensitive adhesive sheet >

The waterproof cover disclosed herein is characterized in that an adhesive sheet is laminated on the outer peripheral edge of a waterproof film, and an adhesive layer for bonding the adhesive sheet and the waterproof film is composed of an adhesive having a storage modulus G' of 53000Pa or higher at 40 ℃. With the waterproof cover configured as described above, the occurrence of wrinkles in the waterproof film due to the passage of time can be prevented. Hereinafter, the pressure-sensitive adhesive layer for bonding the pressure-sensitive adhesive sheet and the waterproof film may be referred to as a "film bonding pressure-sensitive adhesive layer", and the pressure-sensitive adhesive constituting the film bonding pressure-sensitive adhesive layer may be referred to as a "film bonding pressure-sensitive adhesive".

The reason why such an effect can be obtained is considered as follows, for example. That is, the waterproof film on which the adhesive sheet is laminated has internal stress caused by the processing at the time of manufacturing the waterproof film or at the time of laminating the adhesive sheet. For example, in the waterproof film obtained by rolling in the MD direction and stretching in the TD direction as described above, there is an anisotropic internal stress due to the rolling and the stretching. When a waterproof cover is produced by laminating an adhesive sheet on a waterproof film having such an internal stress, the waterproof film is deformed (typically, shrunk) to relax the internal stress after the lamination, and the relative position of the waterproof film with respect to the adhesive sheet is displaced. Such positional deviation is not generally uniformly performed, but is not uniformly performed due to local stress concentration, the anisotropy of the internal stress, and the like. The uneven positional deviation becomes a main factor of generation of wrinkles on the waterproof film with the lapse of time after the waterproof cover is manufactured. The adhesive having the storage modulus G' has high resistance to deformation in the shear direction (the plane direction of the waterproof film). Therefore, when the adhesive layer bonded to the waterproof film is formed by the adhesive (film bonding adhesive) having the storage modulus G', it is considered that relative positional displacement between the waterproof film and the adhesive sheet is suppressed, and an effect of preventing wrinkles of the waterproof film from occurring due to the passage of time is exhibited. However, the reason is not limited to this.

The waterproof cover disclosed herein may be, for example, a form in which an adhesive sheet is laminated on the outer peripheral edge portion of one surface of a waterproof film as in the waterproof cover 10 shown in fig. 1, or may be, for example, a form in which an adhesive sheet is laminated on the outer peripheral edge portions of one surface and the other surface of a waterproof film as in the waterproof cover 20 shown in fig. 3. The adhesive constituting the adhesive layer bonded to at least one surface of the waterproof film has the storage modulus G' described above, and thus the effect of preventing wrinkles of the waterproof film from occurring due to the passage of time can be exerted. Therefore, in the waterproof cover in which the adhesive sheet is laminated on the outer peripheral edge portions of the one surface and the other surface of the waterproof film, the 40 ℃ storage modulus G 'of the adhesive constituting the adhesive layer bonded to the one surface may be 53000Pa or more, and the 40 ℃ storage modulus G' of the adhesive constituting the adhesive layer bonded to the other surface is not particularly limited. In a preferred embodiment, the adhesive layer bonded to one surface and the adhesive layer bonded to the other surface are both composed of an adhesive having a storage modulus G' of 53000Pa or more at 40 ℃. In this case, the effect of preventing the waterproof film from being wrinkled due to the passage of time can be more effectively exhibited.

In the technique disclosed herein, the storage modulus G ' at 40 ℃ and the storage modulus G ' at 80 ℃ described later (hereinafter, also referred to as "storage modulus G ' at 80 ℃) of the adhesive can be determined by dynamic viscoelasticity measurement. Specifically, an adhesive layer having a thickness of about 2mm and made of an adhesive to be measured was prepared, and the adhesive layer was punched out into a disk shape having a diameter of 7.9mm to prepare a sample for measurement. The sample was held and fixed between parallel plates, and dynamic viscoelasticity measurement was performed using a viscoelasticity tester (for example, TA Instruments inc., ARES or equivalent) under the following conditions to obtain a storage modulus G' at each temperature.

Measurement mode: shear mode

Temperature range: -70 ℃ to 150 DEG C

Temperature increase rate: 5 ℃/min

Measurement frequency: 1Hz

The measurement was also performed by the above-described method in examples described later. The adhesive layer may be formed by applying a corresponding adhesive composition to a release liner and drying or curing the adhesive composition. The pressure-sensitive adhesive layer may be formed by stacking a plurality of pressure-sensitive adhesive layers.

In some embodiments of the waterproof covers disclosed herein, the storage modulus G' at 40 ℃ of the film joining adhesive may be, for example, 60000Pa or more, 70000Pa or more, 85000Pa or more, 100000Pa or more, or 110000Pa or more. When the storage modulus G' is high at 40 ℃, the effect of preventing the relative positional displacement of the water-repellent film with respect to the adhesive sheet tends to be high. The upper limit of the storage modulus G' at 40 ℃ is not particularly limited. In some embodiments, the storage modulus G' at 40 ℃ may be, for example, 500000Pa or less, 300000Pa or less, 200000Pa or less, or 150000Pa or less, from the viewpoint of adhesiveness to a waterproof film (particularly, a porous waterproof film).

The waterproof cover disclosed herein may preferably be implemented in such a manner that the storage modulus G' of the film bonding adhesive at 80 ℃ is, for example, 20000Pa or more. When such a film bonding adhesive is used, even if the adhesive is exposed to high temperatures during storage or use, the waterproof film can be prevented from being displaced appropriately, and the occurrence of wrinkles can be effectively suppressed. In some embodiments, the 80 ℃ storage modulus G' may be, for example, 30000Pa or more, 35000Pa or more, or 40000Pa or more. The upper limit of the storage modulus G' at 80 ℃ is not particularly limited. In some embodiments, the 80 ℃ storage modulus G' may be, for example, 200000Pa or less, 150000Pa or less, 100000Pa or less, or 800000Pa or less, from the viewpoint of easily exhibiting good adhesion to a waterproof film (particularly a porous waterproof film).

The storage modulus G' of the adhesive at 40 ℃ and 80 ℃ can be adjusted by, for example, the composition of the base polymer, the molecular weight, the presence or absence of the crosslinking agent, the use of the tackifier, and the selection of the type and amount thereof. As long as it is a person skilled in the art, how to obtain an adhesive exhibiting the preferred storage modulus G' disclosed herein can be understood based on the description of the present specification and the general technical knowledge.

(Binder)

The type of the adhesive constituting the adhesive layer included in the waterproof cover disclosed herein is not particularly limited. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer containing 1 or 2 or more kinds of pressure-sensitive adhesives selected from known various pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives (natural rubber-based, synthetic rubber-based, and mixed systems thereof), silicone pressure-sensitive adhesives, polyester pressure-sensitive adhesives, urethane pressure-sensitive adhesives, polyether pressure-sensitive adhesives, polyamide pressure-sensitive adhesives, and fluorine pressure-sensitive adhesives. Here, the acrylic adhesive refers to an adhesive containing an acrylic polymer as a base polymer. The same applies to rubber-based adhesives and other adhesives.

In some cases, an acrylic adhesive containing an acrylic polymer as a base polymer may be preferably used. The acrylic pressure-sensitive adhesive can easily realize the preferable storage modulus G' at 40 ℃ described in the specification, and can easily adjust the degree of crosslinking and the gel fraction. Thus, it is suitable as a film bonding adhesive for the waterproof cover disclosed herein. Hereinafter, an acrylic adhesive will be mainly described, but the adhesive constituting the adhesive layer of the waterproof cover disclosed herein is not limited to the acrylic adhesive.

(acrylic acid Polymer)

The acrylic polymer as the base polymer of the acrylic adhesive is preferably a polymer containing an alkyl (meth) acrylate as a main monomer and, if necessary, a monomer component which may further contain a sub-monomer copolymerizable with the main monomer. The main monomer herein means a main component in a monomer component constituting the acrylic polymer, that is, a component having a content of more than 50% by weight in the monomer component.

As the alkyl (meth) acrylate, for example, a compound represented by the following formula (1) can be suitably used.

CH₂＝C(R¹)COOR²(1)

Here, R in the above formula (1)¹Is a hydrogen atom or a methyl group. In addition, R²Is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of carbon atoms is sometimes referred to as "C_1-20". ). From the viewpoint of ease of adjustment of the adhesive properties, etc., R is preferable²Is C_1-14The alkyl (meth) acrylate of (meth) acrylic acid chain alkyl group of (1), more preferably R²Is C_1-10An alkyl (meth) acrylate having a chain alkyl group of (1).

As R²Is C_1-20Specific examples of the alkyl (meth) acrylate having a chain alkyl group in (a) are not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, Tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like. These alkyl (meth) acrylates may be used singly in 1 kind or in combination in 2 or more kinds. Suitable examples of the alkyl (meth) acrylate include n-butyl acrylate (n-butyl acrylate)BA) and 2-ethylhexyl acrylate (2 EHA).

The proportion of the alkyl (meth) acrylate in the monomer component is typically more than 50% by weight, and may be, for example, 70% by weight or more, 85% by weight or more, or 90% by weight or more. The proportion of the alkyl (meth) acrylate in the monomer component may be less than 100% by weight, and usually not more than 99.5% by weight is suitable, and may be not more than 98% by weight or not more than 97% by weight, from the viewpoint of facilitating formation of a pressure-sensitive adhesive layer having an appropriate aggregation property.

The technique disclosed herein may preferably contain 50 wt% or more of (meth) acrylic acid C in the monomer component_1-4Alkyl ester mode. The acrylic polymer tends to form a pressure-sensitive adhesive layer having higher resistance to deformation in the shear direction than an acrylic polymer containing, as a main monomer, a (meth) acrylate having an alkyl group having 5 or more carbon atoms at the ester end. In some embodiments, the (meth) acrylic acid C_1-4The proportion of the alkyl ester in the monomer component may be, for example, 70% by weight or more, 75% by weight or more, 85% by weight or more, or 90% by weight or more.

The technique disclosed herein can preferably include 50 wt% or more (for example, 70 wt% or more, 75 wt% or more, 85 wt% or more, or 90 wt% or more) of acrylic acid C in the monomer component_2-4Alkyl ester mode. As acrylic acid C_2-4Specific examples of the alkyl ester include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-Butyl Acrylate (BA), isobutyl acrylate, sec-butyl acrylate and tert-butyl acrylate. Acrylic acid C_2-4The alkyl ester may be used alone in 1 kind or in combination of 2 or more kinds. Among them, preferred is an embodiment in which the monomer component contains more than 50% by weight (for example, 70% by weight or more, 75% by weight or more, 85% by weight or more, or 90% by weight or more) of BA. On the other hand, from the viewpoint of easy formation of a pressure-sensitive adhesive layer having appropriate aggregation properties, (meth) acrylic acid C_1-4Alkyl esters in monomersThe proportion of the component (c) is usually preferably 99.5% by weight or less, and may be 98% by weight or less, or may be less than 97% by weight.

The secondary monomer copolymerizable with the alkyl (meth) acrylate as the main monomer may contribute to introduction of a crosslinking point into the acrylic polymer or increase the cohesive force of the acrylic polymer. The secondary monomer may also contribute to the adjustment of the storage modulus G'. As the auxiliary monomer, for example, 1 kind of monomer or 2 or more kinds of monomers having a functional group shown below can be used alone or in combination.

Carboxyl group-containing monomer: ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid and isocrotonic acid; ethylenically unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and citraconic acid, and anhydrides thereof (maleic anhydride, itaconic anhydride, and the like).

Hydroxyl group-containing monomer: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono (meth) acrylate.

Amide group-containing monomer: such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide.

Amino group-containing monomers: for example, aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate.

Monomer having epoxy group: such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether.

A cyano group-containing monomer: such as acrylonitrile, methacrylonitrile.

A ketone group-containing monomer: such as diacetone (meth) acrylamide, diacetone (meth) acrylate, methyl vinyl ketone, ethyl vinyl ketone, allyl acetoacetate, vinyl acetoacetate.

Monomer having nitrogen atom-containing ring: such as N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine.

Alkoxysilyl group-containing monomer: for example, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane.

When the monomer component contains the functional group-containing monomer as described above, the content of the functional group-containing monomer in the monomer component is not particularly limited. From the viewpoint of appropriately exerting the effect of the functional group-containing monomer, the content of the functional group-containing monomer in the monomer component may be, for example, 0.05% by weight or more, and is preferably 0.1% by weight or more, and may be 0.2% by weight or more, 0.5% by weight or more, or 1% by weight or more. From the viewpoint of easily obtaining the balance of adhesive properties, the content of the functional group-containing monomer in the monomer component is usually preferably 40% by weight or less, and preferably 20% by weight or less, and may be 15% by weight or less, 10% by weight or less, or 7% by weight or less.

In some embodiments, the monomer component preferably contains at least a carboxyl group-containing monomer as the functional group-containing monomer. By including the carboxyl group-containing monomer in the monomer component, the pressure-sensitive adhesive layer having high resistance to deformation in the shear direction can be easily obtained. The carboxyl group-containing monomers may be used alone in 1 kind or in combination in 2 kinds. Among them, preferable carboxyl group-containing monomers include Acrylic Acid (AA) and methacrylic acid (MAA). AA is particularly preferred.

When a carboxyl group-containing monomer is used as the functional group-containing monomer, the amount of the carboxyl group-containing monomer used may be, for example, 0.2% by weight or more (typically, 0.5% by weight or more), and is preferably 1% by weight or more, and may be 2% by weight or more, or may be 3% by weight or more of the monomer component. When the content of the carboxyl group-containing monomer exceeds 3 wt%, a higher effect (for example, an effect of improving the resistance to deformation in the shear direction) is exhibited, and a psa sheet having excellent performance of preventing the positional deviation of the waterproofing membrane can be realized. From the above viewpoint, in one embodiment, the content of the carboxyl group-containing monomer may be 3.2% by weight or more, 3.5% by weight or more, 4% by weight or more, 4.5% by weight or more, or 4.8% by weight or more of the monomer component. The technique disclosed herein can also be preferably carried out using a binder in which the content of the carboxyl group-containing monomer is 5% by weight or more or 8% by weight or more of the monomer component. The upper limit of the content of the carboxyl group-containing monomer is not particularly limited. In some embodiments, the content of the carboxyl group-containing monomer in the monomer component may be, for example, 15 wt% or less, or 12 wt% or less, from the viewpoint of improving the hydrophobicity of the binder. In the technique disclosed herein, the content of the carboxyl group-containing monomer may be 10 wt% or less of the monomer component, and may be preferably carried out using a binder in an amount of 7 wt% or less or 6 wt% or less.

In some embodiments, the monomer component is preferably substantially free of hydroxyl-containing monomers. Here, the monomer component substantially free of a hydroxyl group-containing monomer means that at least a hydroxyl group-containing monomer is not used intentionally, and is a mode that allows, for example, about 0.02 wt% or less (typically about 0.01 wt% or less) of a hydroxyl group-containing monomer to be contained unintentionally in addition to a mode that does not contain a hydroxyl group-containing monomer at all in the monomer component. The technique disclosed herein can be preferably carried out, for example, in such a manner that the monomer component contains a carboxyl group-containing monomer and does not substantially contain a hydroxyl group-containing monomer.

In some embodiments, the monomer component preferably comprises a carboxyl group-containing monomer and is substantially free of other functional group-containing monomers (i.e., other than the carboxyl group-containing monomer). Here, the fact that the monomer component does not substantially contain another functional group-containing monomer means that at least another functional group-containing monomer is not used intentionally, and the monomer component is allowed to contain, for example, about 0.02 wt% or less (typically about 0.01 wt% or less) of another functional group-containing monomer unintentionally, in addition to the embodiment that the monomer component does not contain any other functional group-containing monomer at all.

For the purpose of improving the cohesive force or the like, the monomer component may contain, as a sub-monomer, another copolymerizable monomer other than the functional group-containing monomers exemplified above. Examples of the other copolymerizable monomer include vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene (α -methylstyrene, etc.), vinyl toluene, etc.; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, and isobornyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as aryl (meth) acrylates (e.g., phenyl (meth) acrylate), aryloxyalkyl (meth) acrylates (e.g., phenoxyethyl (meth) acrylate), and arylalkyl (meth) acrylates (e.g., benzyl (meth) acrylate); olefin monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; and the like.

The monomer component may contain a polyfunctional monomer as the above-mentioned other copolymerizable monomer for the purpose of crosslinking or the like. Examples of such a polyfunctional monomer include monomers having 2 or more (for example, 3 or more) polymerizable functional groups in 1 molecule, such as 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. The polymerizable functional group is typically a (meth) acryloyl group. The polyfunctional monomer may be used alone in 1 kind or in combination of 2 or more kinds.

The amount of the other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the purpose and the application, but is usually appropriately 0.01% by weight or more, and may be 0.05% by weight or more, or may be 0.5% by weight or more, from the viewpoint of appropriately exerting the effect of the use. From the viewpoint of easily obtaining the balance of adhesive properties, the content of the other copolymerizable monomer in the monomer component is usually preferably 20% by weight or less, and may be 10% by weight or less, 5% by weight or less, or 1% by weight or less. The technique disclosed herein can be preferably carried out in such a manner that the monomer component does not substantially contain another copolymerizable monomer.

The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as a method for synthesizing an acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method, can be suitably used. For example, the solution polymerization method can be preferably employed. The polymerization temperature in the solution polymerization may be suitably selected depending on the kind of the monomer and the solvent used, the kind of the polymerization initiator, and the like, and may be, for example, about 20 to 170 ℃ (typically about 40 to 140 ℃).

The solvent (polymerization solvent) used for the solution polymerization can be appropriately selected from conventionally known organic solvents. For example, aromatic compounds (typically, aromatic hydrocarbons) selected from toluene and the like; acetic acid esters such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; halogenated alkanes such as 1, 2-dichloroethane; lower alcohols (e.g., monohydric alcohols having 1 to 4 carbon atoms) such as isopropyl alcohol; ethers such as t-butyl methyl ether; ketones such as methyl ethyl ketone; etc. or a mixed solvent of 2 or more.

The initiator used for the polymerization may be suitably selected from conventionally known polymerization initiators depending on the kind of the polymerization method. For example, 1 or 2 or more azo polymerization initiators such as 2, 2' -Azobisisobutyronitrile (AIBN) can be preferably used. Other examples of the polymerization initiator include persulfates such as potassium persulfate; peroxide initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane initiators such as phenyl-substituted ethane; an aromatic carbonyl compound; and the like. As another example of the polymerization initiator, a redox initiator based on a combination of a peroxide and a reducing agent can be cited. Such polymerization initiators may be used alone in 1 kind or in combination of 2 or more kinds. The amount of the polymerization initiator to be used may be any amount as long as it is usually used, and may be selected from the range of about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) per 100 parts by weight of the monomer component.

The solution polymerization described above can provide a polymerization reaction solution in which an acrylic polymer is dissolved in an organic solvent. The pressure-sensitive adhesive layer in the technology disclosed herein may be formed from a pressure-sensitive adhesive composition containing the above-mentioned polymerization reaction liquid or an acrylic polymer solution obtained by subjecting the reaction liquid to appropriate post-treatment. As the acrylic polymer solution, a solution prepared by preparing the polymerization reaction solution to an appropriate viscosity (concentration) as needed can be used. Alternatively, an acrylic polymer solution prepared by synthesizing an acrylic polymer by a polymerization method other than solution polymerization (for example, emulsion polymerization, photopolymerization, bulk polymerization, or the like) and dissolving the acrylic polymer in an organic solvent may be used.

(Tg of base Polymer)

In the techniques disclosed herein, the base polymer (e.g., acrylic polymer) of the adhesive is preferably designed such that the glass transition temperature (Tg) of the polymer is about-15 ℃ or less (e.g., about-70 ℃ or more and-15 ℃ or less). Herein, the Tg of a polymer refers to the Tg obtained by the Fox equation based on the composition of monomer components used for synthesizing the polymer. The Fox formula is a relational expression between Tg of a copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing monomers constituting the copolymer.

1/Tg＝Σ(Wi/Tgi)

In the above Fox formula, Tg represents the glass transition temperature (unit: K) of the copolymer, Wi represents the weight fraction of the monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi represents the glass transition temperature (unit: K) of the homopolymer of the monomer i.

The glass transition temperature of the homopolymer used for calculating the Tg is the value described in the publicly known data. For example, the following values are used for the monomers listed below as the glass transition temperatures of the homopolymers of the monomers.

Regarding the glass transition temperature of a homopolymer of a monomer other than those exemplified above, the values described in "Polymer Handbook" (3 rd edition, John Wiley & Sons, inc., 1989) were used. The highest value is used for monomers having various values described in this document. In the case where the above-mentioned Polymer Handbook is not described, a value obtained by the measurement method described in Japanese patent application laid-open No. 2007-51271 is used.

In some embodiments, the Tg of the base polymer may be, for example, -70 ℃ or higher, and is generally preferably-65 ℃ or higher. When the Tg of the base polymer is high, the resistance to deformation in the shear direction tends to be improved. In some preferred embodiments, the Tg of the base polymer may be-60 ℃ or higher, or may be-55 ℃ or higher. From the viewpoint of adhesion to an adherend (for example, a waterproof film of a laminated adhesive sheet), the Tg of the base polymer is usually favorably not more than-25 ℃ and may be, for example, not more than-35 ℃, not more than-40 ℃ or not more than-45 ℃.

The weight average molecular weight (Mw) of the base polymer (suitably, acrylic polymer) is not particularly limited, and may be, for example, about 10X 10⁴～500×10⁴The range of (1). From the viewpoint of adhesive properties, the Mw of the base polymer is preferably at about 30X 10⁴～200×10⁴(more preferably about 45X 10)⁴～150×10⁴Typically about 65X 10⁴～130×10⁴) The range of (1). Herein, Mw is a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography). As the GPC apparatus, for example, the model "HLC-8320 GPC" (column: TSK gel GMH-H (S), manufactured by Tosoh corporation) can be used.

(crosslinking agent)

The adhesive layer in the technology disclosed herein may be composed of a crosslinked adhesive. Crosslinking the adhesive may be a means useful for adjusting the storage modulus G' of the adhesive layer to the appropriate range disclosed herein.

The kind of the crosslinking agent is not particularly limited, and can be suitably selected and used from, for example, an epoxy crosslinking agent, an isocyanate crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a melamine crosslinking agent, a carbodiimide crosslinking agent, a hydrazine crosslinking agent, a metal chelate crosslinking agent, a silane coupling agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal salt crosslinking agent, an amine crosslinking agent, and the like. The crosslinking agent may be used alone in 1 kind or in combination of 2 or more kinds. Among them, preferable crosslinking agents include epoxy crosslinking agents and isocyanate crosslinking agents. These may be used alone, or an epoxy-based crosslinking agent and an isocyanate-based crosslinking agent may be used in combination as described later.

As the epoxy crosslinking agent, a compound having 2 or more epoxy groups in 1 molecule can be used without particular limitation. Preferably an epoxy crosslinking agent having 3 to 5 epoxy groups in 1 molecule. The epoxy crosslinking agent may be used alone in 1 kind or in combination of 2 or more kinds. Specific examples of the epoxy-based crosslinking agent include N, N' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polyglycerol polyglycidyl ether. Commercially available products of the epoxy-based crosslinking agent include a trade name "TETRAD-C" and a trade name "TETRAD-X" manufactured by Mitsubishi gas chemical Corporation, a trade name "EPICLON CR-5L" manufactured by DIC Corporation, a trade name "DENACOL EX-512" manufactured by Nagase ChemteX Corporation, and a trade name "TEPIC-G" manufactured by Nissan chemical Corporation.

As the isocyanate-based crosslinking agent, polyfunctional isocyanates (compounds having an average of 2 or more isocyanate groups per molecule, including those having an isocyanurate structure) can be preferably used. The isocyanate-based crosslinking agent may be used alone in 1 kind or in combination of 2 or more kinds. Polyfunctional isocyanates having an average of 3 or more isocyanate groups per molecule are preferred. The 3 or more functional isocyanate may be a polymer (typically a dimer or trimer) of a2 or 3 or more functional isocyanate, a derivative (for example, an addition reaction product of a polyol and 2 or more molecules of a polyfunctional isocyanate), a polymer, or the like. Examples thereof include: a dimer or trimer of diphenylmethane diisocyanate, an isocyanurate body of hexamethylene diisocyanate (a trimer adduct of an isocyanurate structure), a reaction product of trimethylolpropane and tolylene diisocyanate, a reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, and other polyfunctional isocyanates. As commercially available products of the polyfunctional isocyanate, there can be mentioned: the trade name "DURANATE TPA-100" manufactured by Asahi Kasei K.K., the trade name "CORONATE L", "CORONATE HL", "CORONATE HK", "CORONATE HX", "CORONATE 2096" manufactured by Tosoh chemical Co., Ltd., trade name "TAKENATE L" and the like.

As the oxazoline-based crosslinking agent, a crosslinking agent having 1 or more oxazoline groups in 1 molecule can be used without particular limitation. The oxazoline group may be any of a 2-oxazoline group, a 3-oxazoline group and a 4-oxazoline group. In general, an oxazoline-based crosslinking agent having a 2-oxazoline group can be preferably used.

Examples of the aziridine-based crosslinking agent include trimethylolpropane tris [ 3- (1-aziridinyl) propionate ], trimethylolpropane tris [ 3- (1- (2-methyl) aziridinyl propionate) ].

Examples of the melamine-based crosslinking agent include hexamethylolmelamine and butylated melamine resin.

Examples of the carbodiimide-based crosslinking agent include carbodiimide V series such as carbodiimide V-02, carbodiimide V-02-L2, and carbodiimide V-04; CARBODILITE E-01, CARBODILITE E-02, CARBODILITE E-04, and other CARBODILITE E series; the CARBODILITE series (manufactured by Nisshin Kagaku K.K.); and the like are commercially available.

The hydrazine-based crosslinking agent contains a hydrazine group (H)₂N-NH-) as the crosslinkable functional group, specific examples thereof include polycarboxylic acid polyhydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide and adipic acid dihydrazide, and hydantoins such as 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin.

Examples of the metal chelate-based crosslinking agent include an aluminum chelate-based compound, a titanium chelate-based compound, a zinc chelate-based compound, a zirconium chelate-based compound, an iron chelate-based compound, a cobalt chelate-based compound, a nickel chelate-based compound, a tin chelate-based compound, a manganese chelate-based compound, and a chromium chelate-based compound.

As the silane coupling agent, a known silane coupling agent having a silicon (Si) -containing group (typically, an alkoxysilyl group) as a crosslinkable functional group can be used. Non-limiting examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-aminopropyltrimethoxysilane.

The amount of the epoxy crosslinking agent used is not particularly limited, and may be, for example, more than 0 part by weight and 1 part by weight or less based on 100 parts by weight of the base polymer. The amount of the epoxy crosslinking agent used may be, for example, 0.001 part by weight or more, 0.002 part by weight or more, 0.005 part by weight or more, or 0.007 part by weight or more, based on 100 parts by weight of the base polymer. The storage modulus G' of the adhesive tends to be high as the amount of the crosslinking agent used increases. From the viewpoint of improving adhesion to an adherend (for example, a waterproof film), the amount of the epoxy-based crosslinking agent used is usually preferably 0.5 parts by weight or less, and may be 0.3 parts by weight or less, or may be less than 0.2 parts by weight, based on 100 parts by weight of the base polymer. In some embodiments, the amount of the epoxy crosslinking agent used may be less than 0.1 part by weight or less than 0.08 part by weight based on 100 parts by weight of the base polymer.

The amount of the isocyanate-based crosslinking agent used is not particularly limited, and may be, for example, more than 0 part by weight and 10 parts by weight or less based on 100 parts by weight of the base polymer. The amount of the isocyanate-based crosslinking agent used may be, for example, 0.1 part by weight or more, 0.5 part by weight or more, 0.7 part by weight or more, or 0.9 part by weight or more, based on 100 parts by weight of the base polymer. The storage modulus G' of the adhesive tends to be high as the amount of the crosslinking agent used increases. From the viewpoint of improving adhesion to an adherend (for example, a waterproof film), the amount of the isocyanate-based crosslinking agent used is preferably 10 parts by weight or less, and may be 8 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less, based on 100 parts by weight of the base polymer. In some embodiments, the amount of the isocyanate-based crosslinking agent used may be less than 3 parts by weight, 2.5 parts by weight or less, or 2.1 parts by weight or less, based on 100 parts by weight of the base polymer. The technique disclosed herein can be suitably carried out in such a manner that the amount of the isocyanate-based crosslinking agent used is 1.8 parts by weight or less, 1.5 parts by weight or less, or 1.2 parts by weight or less, relative to 100 parts by weight of the base polymer.

In some versions of the technology disclosed herein, the film joining adhesive is preferably crosslinked with at least an epoxy-based crosslinking agent. By using the epoxy crosslinking agent, the occurrence of wrinkles in the waterproof film due to the passage of time can be suitably suppressed. In some preferred embodiments, an epoxy-based crosslinking agent and a non-epoxy-based crosslinking agent may be used in combination. This can appropriately balance the storage modulus G' of the pressure-sensitive adhesive and the adhesiveness to an adherend, and can more effectively suppress the occurrence of wrinkles in the waterproof film over time. The non-epoxy crosslinking agent may be arbitrarily selected from the above-mentioned crosslinking agents except for the epoxy crosslinking agent. For example, an isocyanate-based crosslinking agent can be preferably used as the non-epoxy-based crosslinking agent.

When the epoxy-based crosslinking agent and the non-epoxy-based crosslinking agent (for example, an isocyanate-based crosslinking agent) are used in combination, the relationship between the amount of the epoxy-based crosslinking agent and the amount of the non-epoxy-based crosslinking agent is not particularly limited. In some embodiments, the amount of the epoxy-based crosslinking agent may be, for example, 1 time or more, 5 times or more, 10 times or more, 50 times or more, 100 times or more, or 150 times or more the amount of the non-epoxy-based crosslinking agent on a weight basis. The amount of the epoxy-based crosslinking agent to be used may be, for example, 500 times or less, 250 times or less, 200 times or less, 130 times or less, or 80 times or less the amount of the non-epoxy-based crosslinking agent to be used on a weight basis.

(tackifier)

The adhesive may contain a tackifier. This can improve the adhesiveness to an adherend (for example, a waterproof film). In addition, a tackifier can be used, whereby the storage modulus G' of the adhesive can be adjusted to an appropriate range, and the resistance to deformation in the shear direction can be improved. By appropriately using a tackifier, these effects complement each other, and the performance of suppressing the relative positional deviation between the pressure-sensitive adhesive sheet and the adherend can be effectively improved. As the tackifier, a tackifier resin, an acrylic oligomer, or the like can be used. The tackifier may be used singly or in combination of two or more. The amount of the tackifier to be used may be, for example, 1 part by weight or more and 150 parts by weight or less, 1 part by weight or more and 50 parts by weight or less, or 5 parts by weight or more and less than 40 parts by weight with respect to 100 parts by weight of the base polymer.

As the tackifier resin, 1 or 2 or more kinds selected from known various tackifier resins such as a phenol-based tackifier resin, a terpene-based tackifier resin, a modified terpene-based tackifier resin, a rosin-based tackifier resin, and a hydrocarbon-based tackifier resin can be used.

Examples of the phenolic tackifying resins include terpene phenol resins, hydrogenated terpene phenol resins, alkyl phenol resins, and rosin phenol resins.

The terpene-phenol resin is a polymer containing a terpene residue and a phenol residue, and is a concept including both a copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin) and a resin obtained by phenol-modifying a homopolymer or a copolymer of a terpene (phenol-modified terpene resin). Suitable examples of terpenes constituting such a terpene-phenol resin include: monoterpenes such as α -pinene, β -pinene, limonene (including d-isomer, l-isomer, and d/l-isomer (dipentene)). The hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. Sometimes also referred to as hydrogenated terpene phenol resins.

The alkylphenol resin is a resin (oleo-phenolic resin) obtained from alkylphenol and formaldehyde. Examples of the alkylphenol resin include novolak type and resol type.

The rosin phenol resin is typically a rosin or a phenol-modified product of the above rosin derivatives (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters). Examples of the rosin phenol resin include rosin phenol resins obtained by a method of adding phenol to rosins or the above various rosin derivatives with an acid catalyst and performing thermal polymerization, and the like.

Examples of the terpene-based tackifier resin include polymers of terpenes (typically, monoterpenes) such as α -pinene, β -pinene, d-limonene, l-limonene, and dipentene. The terpene may be a homopolymer of 1 kind of terpene, or a copolymer of 2 or more kinds of terpenes. Examples of the homopolymer of 1 terpene include an α -pinene polymer, a β -pinene polymer, and a dipentene polymer. Examples of the modified terpene-based tackifier resin include those obtained by modifying the above terpene resins. Specifically, a styrene-modified terpene resin, a hydrogenated terpene resin, and the like can be exemplified.

The rosin-based tackifier resin referred to herein includes both rosin-based resins and rosin derivative resins. Examples of rosins include: unmodified rosins (raw rosins) such as gum rosin, wood rosin, tall oil rosin and the like; modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, other chemically modified rosins, etc.) obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, etc.

Rosin derivative resins are typically derivatives of such rosins as described above. The rosin-based resin referred to herein includes derivatives of unmodified rosins and derivatives of modified rosins (including hydrogenated rosins, disproportionated rosins and polymerized rosins). Examples thereof include: rosin esters such as an unmodified rosin ester as an ester of an unmodified rosin and an alcohol, and a modified rosin ester as an ester of a modified rosin and an alcohol; for example, unsaturated fatty acid-modified rosins obtained by modifying rosins with unsaturated fatty acids; for example, unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; for example, rosin alcohols obtained by reducing carboxyl groups of rosins or the various rosin derivatives described above (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters); for example, metal salts of rosins or various rosin derivatives described above; and the like. Specific examples of rosin esters include: methyl esters, triethylene glycol esters, glycerol esters, pentaerythritol esters, and the like of unmodified rosins or modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, and the like).

Examples of the hydrocarbon-based tackifier resin include: various hydrocarbon-based resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene/olefin copolymers, etc.), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, and coumarone/indene-based resins.

The softening point of the tackifier resin is not particularly limited. From the viewpoint of improving the storage modulus G', it is generally preferable to use a tackifier resin having a softening point (softening temperature) of 90 ℃ or higher, more preferably 115 ℃ or higher, for example 130 ℃ or higher. A tackifier resin (e.g., terpene-phenol resin) having a softening point of 135 ℃ or higher or 140 ℃ or higher may also be used. The technique disclosed herein can be preferably carried out in such a manner that more than 50% by weight, preferably more than 70% by weight, and more preferably more than 90% by weight of the total amount of the tackifier resins used are tackifier resins having the above softening points. The upper limit of the softening point of the tackifier resin is not particularly limited. In one embodiment, a tackifier resin having a softening point of 200 ℃ or less (more preferably 180 ℃ or less) can be preferably used from the viewpoint of improving adhesiveness to an adherend. The softening point of the tackifier resin can be measured according to the softening point test method (ring and ball method) specified in JIS K2207.

The amount of the tackifier resin to be used is not particularly limited, and may be appropriately set, for example, within a range of 1 part by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the base polymer (for example, acrylic polymer). From the viewpoint of suitably exhibiting the effect of improving the adhesiveness to an adherend, the amount of the tackifier resin used is usually suitably 5 parts by weight or more, and may be 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, and 25 parts by weight or more, relative to 100 parts by weight of the base polymer. When the amount of the tackifier resin used is large, the storage modulus G' tends to be high. From the viewpoint of adhesion to an adherend and heat-resistant cohesive strength, the amount of the tackifier resin used is usually preferably 80 parts by weight or less, and may be 50 parts by weight or less, less than 40 parts by weight, or less than 35 parts by weight, based on 100 parts by weight of the base polymer.

Acrylic oligomers may be used as tackifiers. As the acrylic oligomer, a polymer having a Tg of typically 0 ℃ or higher, which is a polymer of a monomer component containing more than 50% by weight of an acrylic monomer, can be used. From the viewpoint of compatibility, the acrylic oligomer is particularly preferably used as a tackifier in an acrylic adhesive.

The Tg of the acrylic oligomer is preferably in the range of usually 0 ℃ to 300 ℃. With the acrylic oligomer having Tg within the above range, the waterproof film tends to be suppressed from wrinkling appropriately. From the viewpoint of improving the storage modulus G', the Tg of the acrylic oligomer may be, for example, 25 ℃ or higher, 40 ℃ or higher, 50 ℃ or higher, or 60 ℃ or higher in some embodiments. In some embodiments, the Tg of the acrylic oligomer may be, for example, 200 ℃ or less, 150 ℃ or less, 120 ℃ or less, 100 ℃ or less, or 80 ℃ or less, from the viewpoint of adhesion to an adherend. The Tg of the acrylic oligomer is the same as that of the base polymer, and is a value calculated based on the Fox equation.

The weight average molecular weight (Mw) of the acrylic oligomer may be, for example, 1000 or more and less than 30000. When Mw is within the above range, the adhesiveness to an adherend can be effectively improved while suppressing a decrease in cohesive force. In some preferred embodiments, the Mw of the acrylic oligomer may be, for example, 1500 or more, 2000 or more, 2500 or more, or 3000 or more. In some embodiments, the Mw of the acrylic oligomer may be, for example, less than 20000, less than 10000, 7000 or less, 5000 or less, 4500 or less, or 4000 or less from the viewpoint of adhesion to an adherend and compatibility. The Mw of the acrylic oligomer can be measured by Gel Permeation Chromatography (GPC) and determined as a value in terms of standard polystyrene.

Examples of the monomer constituting the acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate; esters of (meth) acrylic acid and alicyclic alcohol (alicyclic hydrocarbon group-containing (meth) acrylic acid esters) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; (meth) acrylic acid esters derived from alcohols which are terpene compound derivatives; and the like (meth) acrylates (i.e., (meth) acrylates). Such (meth) acrylates may be used singly in 1 kind or in combination in 2 or more kinds.

From the viewpoint of improving the resistance to deformation in the shear direction, the acrylic oligomer preferably contains an alkyl (meth) acrylate having a branched structure with an alkyl group such as isobutyl (meth) acrylate or tert-butyl (meth) acrylate; esters of (meth) acrylic acid and alicyclic alcohol (alicyclic hydrocarbon group-containing (meth) acrylic acid esters) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; an acrylic monomer having a bulky structure represented by a (meth) acrylate having a cyclic structure such as an aryl (meth) acrylate like phenyl (meth) acrylate or benzyl (meth) acrylate is used as a monomer unit. In addition, when ultraviolet light is used for synthesizing the acrylic oligomer or for producing the pressure-sensitive adhesive layer, it is preferable that the monomer has a saturated bond since it is not likely to cause polymerization inhibition, and an alkyl (meth) acrylate in which an alkyl group has a branched structure or an ester with an alicyclic alcohol (an alicyclic hydrocarbon group-containing (meth) acrylate) may be suitably used as the monomer constituting the acrylic oligomer. The branched alkyl (meth) acrylate, alicyclic hydrocarbon (meth) acrylate, and aryl (meth) acrylate described above are all (meth) acrylate monomers in the art disclosed herein. The alicyclic hydrocarbon group may be a saturated or unsaturated alicyclic hydrocarbon group.

The proportion of the (meth) acrylate monomer (for example, alicyclic hydrocarbon group-containing (meth) acrylate) in the entire monomer components constituting the acrylic oligomer is typically more than 50% by weight, preferably 60% by weight or more, more preferably 70% by weight or more, and may be 80% by weight or more, or may be 90% by weight or more. The acrylic oligomer may have a monomer composition substantially formed only of a (meth) acrylate monomer.

As the constituent monomer component of the acrylic oligomer, a functional group-containing monomer may be used in addition to the (meth) acrylate monomer. The functional group-containing monomer can contribute to improvement of at least one of compatibility with the base polymer, aggregability of the pressure-sensitive adhesive, adhesiveness to an adherend, and the like. Suitable examples of the functional group-containing monomer include monomers having a nitrogen atom-containing ring (typically, a nitrogen atom-containing heterocycle), such as N-vinyl-2-pyrrolidone and N-acryloylmorpholine; amino group-containing monomers such as N, N-dimethylaminoethyl (meth) acrylate; amide group-containing monomers such as N, N-diethyl (meth) acrylamide; AA. Carboxyl group-containing monomers such as MAA; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate. These functional group-containing monomers may be used alone in 1 kind or in combination of 2 or more kinds. Among them, carboxyl group-containing monomers are preferable, and AA is particularly preferable.

When the monomer component constituting the acrylic oligomer contains a functional group-containing monomer, the proportion of the functional group-containing monomer (for example, a carboxyl group-containing monomer such as AA) in the entire monomer component may be, for example, 0.5% by weight or more, 1% by weight or more, 2% by weight or more, or 3% by weight or more. The proportion of the functional group-containing monomer is typically less than 50% by weight, and is usually preferably 40% by weight or less, and may be 25% by weight or less, 15% by weight or less, 10% by weight or less, or 7% by weight or less, from the viewpoint of adhesion to an adherend and the like.

The acrylic oligomer can be formed by polymerizing its constituent monomer components. The polymerization method and polymerization method are not particularly limited, and various conventionally known polymerization methods (for example, solution polymerization, emulsion polymerization, bulk polymerization, photopolymerization, and radiation polymerization) can be used in a suitable manner. The kind of the polymerization initiator (for example, azo polymerization initiator such as AIBN) which can be used as needed is roughly as exemplified in the synthesis of acrylic polymers, and the amount of the polymerization initiator and the amount of the chain transfer agent such as n-dodecylmercaptan which is optionally used are appropriately set based on the technical common knowledge so as to have a desired molecular weight, and therefore, detailed description thereof is omitted here.

From the above-mentioned viewpoints, examples of suitable acrylic oligomers include homopolymers of dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), dicyclopentanyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), and 1-adamantyl acrylate (ADA), examples thereof include a copolymer of CHMA and isobutyl methacrylate (IBMA), a copolymer of CHMA and IBXMA, a copolymer of CHMA and Acryloylmorpholine (ACMO), a copolymer of CHMA and Diethylacrylamide (DEAA), a copolymer of CHMA and AA, a copolymer of ADA and Methyl Methacrylate (MMA), a copolymer of DCPMA and IBXMA, a copolymer of DCPMA and MMA, a copolymer of any of the above-mentioned (meth) acrylates and AA, and a copolymer of AA and a monomer constituting any of the above-mentioned copolymers.

The amount of the acrylic oligomer used may be, for example, 1 part by weight or more per 100 parts by weight of the base polymer (for example, acrylic polymer). From the viewpoint of more effectively exhibiting the effects of the acrylic oligomer, the amount of the acrylic oligomer used may be, for example, 5 parts by weight or more, 8 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. From the viewpoint of compatibility with the base polymer, the content of the acrylic oligomer is usually preferably 50 parts by weight or less, and may be 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less.

(other additives)

The binder may contain, in addition to the above components, various additives generally used in the field of binders such as a leveling agent, a crosslinking aid, a plasticizer, a softening agent, a pigment, a colorant such as a dye, an antistatic agent, an antioxidant, an ultraviolet absorber, an antioxidant, and a light stabilizer, as required. Conventionally known substances can be used as such various additives by conventional methods, and are not characteristic of the present invention, and therefore, detailed descriptions thereof are omitted.

(adhesive layer)

The pressure-sensitive adhesive layer in the waterproof cover disclosed herein may be a pressure-sensitive adhesive layer formed from an aqueous pressure-sensitive adhesive composition, a solvent-based pressure-sensitive adhesive composition, a hot-melt pressure-sensitive adhesive composition, or an active energy ray-curable pressure-sensitive adhesive composition that exerts an effect by irradiation with active energy rays such as ultraviolet rays or electron beams. The aqueous pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition in a form containing a pressure-sensitive adhesive (pressure-sensitive adhesive layer-forming component) in a solvent (aqueous solvent) mainly containing water, and includes an aqueous dispersion type pressure-sensitive adhesive composition (a composition in a form in which at least a part of the pressure-sensitive adhesive is dispersed in water) and an aqueous solution type pressure-sensitive adhesive composition (a composition in a form in which the pressure-sensitive adhesive is dissolved in water). The solvent-based adhesive composition is in a form in which an organic solvent contains an adhesive. From the viewpoint of adhesive properties and the like, the technique disclosed herein can be preferably implemented to include an adhesive layer formed from a solvent-based adhesive composition.

The adhesive layer can be formed by a conventionally known method. For example, a method of forming an adhesive layer by applying an adhesive composition to a surface having releasability (release surface) and drying the adhesive composition can be employed. For example, a method (direct method) of forming an adhesive layer by directly applying (typically, coating) an adhesive composition to a support substrate and drying the adhesive composition can be used for an adhesive sheet having a support substrate structure. In addition, a method (transfer method) of forming an adhesive layer on a surface having releasability (release surface) by applying an adhesive composition to the surface and drying the adhesive composition, and transferring the adhesive layer to a supporting substrate can be employed. As the release surface, for example, a surface of a release liner described later can be preferably used. The pressure-sensitive adhesive layer in the technology disclosed herein is typically formed continuously, but is not limited to this form, and may be formed in a regular or random pattern such as dots or stripes, for example.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be appropriately set, for example, within a range of 1 μm to 150 μm. From the viewpoint of avoiding an excessive thickness of the pressure-sensitive adhesive sheet, the thickness of the pressure-sensitive adhesive layer may be, for example, 100 μm or less, 70 μm or less, or 50 μm or less. From the viewpoint of thinning and workability of the waterproof cover, the thickness of the pressure-sensitive adhesive layer may be, for example, 40 μm or less, 35 μm or less, 30 μm or less, less than 25 μm, 22 μm or less, or 17 μm or less in some embodiments. From the viewpoint of adhesion to an adherend, the thickness of the pressure-sensitive adhesive layer is favorably 3 μm or more, and may be 5 μm or more, 8 μm or more, 10 μm or more, or 15 μm or more. In some embodiments, the thickness of the pressure-sensitive adhesive layer may be 20 μm or more, 25 μm or more, 30 μm or more, or 40 μm or more.

Although not particularly limited, the gel fraction of the pressure-sensitive adhesive layer may be, for example, 10% or more. Here, the gel fraction of the pressure-sensitive adhesive layer was measured by the following method. Specifically, a sample for measurement with a weight of W1 was wrapped in a porous PTFE sheet and immersed in ethyl acetate at room temperature for 1 week. Subsequently, the measurement sample was dried, the weight W2 of the ethyl acetate-insoluble matter was measured, and W1 and W2 were substituted into the following formula to calculate the gel fraction.

Gel fraction (%) ═ W2/W1 × 100;

as the porous PTFE sheet, a product name "NITOFLON NTF 1122" manufactured by ritong electrical corporation or a product equivalent thereof can be used. The measurement was also performed by the above-described method in examples described later.

From the viewpoint of improving the resistance to deformation in the shear direction, the gel fraction is usually favorably 20% or more, and may be 30% or more, 35% or more, 40% or more, or 45% or more. In some embodiments, the gel fraction may be 55% or more, 65% or more, or 75% or more. The upper limit of the gel fraction is 100% in principle. From the viewpoint of adhesion to an adherend, the gel fraction of the pressure-sensitive adhesive layer is usually preferably 95% or less, and may be 90% or less, 85% or less, 80% or less, or 70% or less. The gel fraction of the pressure-sensitive adhesive layer can be adjusted by, for example, selecting the composition, molecular weight, crosslinking agent, presence or absence of use of a tackifier, the type and amount of the tackifier, and the like of the base polymer.

(substrate)

In the technique disclosed herein, the adhesive sheet laminated on the outer peripheral edge portion of the waterproof film may be a substrate-less adhesive sheet formed only of an adhesive layer, or may be a substrate-attached adhesive sheet having an adhesive layer on at least the first surface (waterproof film side surface) of the substrate. The substrate-attached pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive substrate-attached pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on the first surface and the second surface (outer surface) of a substrate, or a single-sided pressure-sensitive adhesive substrate-attached pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer only on the first surface of a substrate.

In the embodiment where the pressure-sensitive adhesive sheet is in the form of a single-sided pressure-sensitive adhesive or double-sided pressure-sensitive adhesive sheet with a substrate, a resin film, paper, cloth, a rubber sheet, a foam sheet, a metal foil, a composite thereof, or the like can be used as the substrate. Examples of the resin film include polyester films; a polyolefin film; vinyl chloride resin films; a vinyl acetate resin film; a polyimide resin film; a polyamide resin film; a polyurethane film; cellophane; and the like. Examples of the paper include japanese paper, kraft paper, glassine paper (glass paper), high-quality paper, synthetic paper, and top-coated paper. Examples of the cloth include woven cloth and nonwoven cloth obtained from various fibrous materials by themselves or by blending. Examples of the fibrous material include cotton, rayon, abaca, pulp (pulp), rayon, acetate, polyester, polyvinyl alcohol, polyamide, and polyolefin. Examples of the rubber sheet include a natural rubber sheet and a butyl rubber sheet. Examples of the foam sheet include a foamed polyolefin sheet, a foamed polyurethane sheet, and a foamed polychloroprene rubber sheet. Examples of the metal foil include aluminum foil and copper foil.

The term "nonwoven fabric" as used herein means a concept of a nonwoven fabric for a psa sheet mainly used in the field of psa tapes and other psa sheets, and typically means a nonwoven fabric (which may be referred to as "paper") produced using a normal paper machine. The resin film referred to herein is typically a non-porous resin sheet, and is a concept distinguished from a nonwoven fabric (i.e., excluding a nonwoven fabric), for example. The resin film may be any of a non-stretched film, a uniaxially stretched film, and a biaxially stretched film.

Suitable examples of the substrate include a resin film and a foam sheet. In some embodiments, a resin film is preferably used from the viewpoint of suppression of deformation in the shear direction of the pressure-sensitive adhesive sheet and processability. Suitable examples of the resin film include a polyester film, a polyolefin film, and a Polyimide (PI) film. Specific examples of the polyester film include a polyethylene terephthalate (PET) film, a polybutylene terephthalate film, a polyethylene naphthalate film, and a polybutylene naphthalate film. Specific examples of the polyolefin film include polypropylene (PP) films such as a non-oriented polypropylene (CPP) film and a biaxially oriented polypropylene (OPP) film; polyethylene (PE) films such as Low Density Polyethylene (LDPE) films, straight-chain low density polyethylene (LLDPE) films, Medium Density Polyethylene (MDPE) films, High Density Polyethylene (HDPE) films, and mixed films of 2 or more types of polyethylene; a PP/PE mixed film is formed by mixing polypropylene and polyethylene. Among them, from the viewpoint of strength and dimensional stability, preferable substrates include PET films and PI films.

The thickness of the base material is not particularly limited. From the viewpoint of thinning of the waterproof cover, the thickness of the base material is usually preferably 200 μm or less, and may be 100 μm or less, 80 μm or less, or 50 μm or less. In some embodiments, the thickness of the substrate may be, for example, 30 μm or less, 20 μm or less, or 10 μm or less. From the viewpoint of handling ability, processability, and the like of the pressure-sensitive adhesive sheet, the thickness of the base material is usually preferably about 2 μm or more, and may be 3 μm or more, or 7 μm or more. In some embodiments, the thickness of the substrate may exceed 10 μm, 15 μm, or 25 μm, for example.

The surface of the substrate may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and coating with a primer. Such surface treatment may be treatment for improving adhesion between the base material and the adhesive layer, in other words, for improving anchoring properties of the adhesive layer to the base material.

(characteristics of adhesive sheet, etc.)

The adhesive sheet disclosed herein preferably exhibits a cohesive force at a level such that the offset distance after 1 hour becomes 0.5mm or less (that is, the offset distance is 0.5 mm/hour or less) in a 40 ℃ holding power test by the method described in examples described later. In some embodiments, the offset distance is preferably 0.4mm or less, more preferably 0.3mm or less, and further preferably 0.2mm or less, and may be less than 0.2mm or may be 0.15mm or less. The prevention cover constructed using the adhesive sheet having a shorter offset distance in the 40 ℃ holding power test tends to suppress the generation of wrinkles in the waterproof film more effectively. The lower limit of the offset distance is 0.0 mm.

The adhesive sheet disclosed herein preferably exhibits a level of cohesive force such that the offset distance after 1 hour becomes 1.0mm or less (that is, the offset distance is 1.0 mm/hour or less) in an 80 ℃ holding power test by the method described in examples described later. In some embodiments, the offset distance is preferably 0.6mm or less, more preferably 0.5mm or less, and further preferably 0.4mm or less, and may be 0.3mm or less, or may be less than 0.3 mm. The prevention cover constructed using the adhesive sheet having a shorter offset distance in the 80 ℃ holding power test tends to suppress the generation of wrinkles in the waterproof film more effectively. The lower limit of the offset distance is 0.0 mm.

In the adhesive sheet disclosed herein, the peel strength to the PTFE porous membrane (peel strength to PTFE) is preferably 2.0N/20mm or more on the adhesive surface on the side joined to the waterproof membrane. The pressure-sensitive adhesive sheet exhibiting such peel strength is suitable for preventing wrinkles in a waterproof film by easily suppressing the positional displacement of the waterproof film. The PTFE peel strength was measured by the method described in the examples described below. In some embodiments, the peel strength may be, for example, 3.0N/20mm or more, or may be 4.0N/20mm or more. The upper limit of the peel strength of PTFE is not particularly limited. In some embodiments, the peel strength may be, for example, 15N/20mm or less, 10N/20mm or less, 8.0N/20mm or less, or 6.0N/20mm or less, from the viewpoint of easily satisfying the preferred storage modulus G' disclosed herein.

The peel strength of PTFE can be measured as follows. That is, the PTFE porous membrane was fixed to the surface of the stainless steel plate with a double-sided pressure-sensitive adhesive tape to be used as an adherend. As the PTFE porous membrane, a PTFE porous membrane produced by the method described in the examples described below or a product equivalent thereof is used. A measurement sample was prepared by cutting the pressure-sensitive adhesive sheet into a size of 20mm in width and 100mm in length, and the pressure-sensitive adhesive surface of the measurement sample was pressure-bonded to the surface of the adherend (the surface of the PTFE porous film) by reciprocating a 2kg roller 1 time at 23 ℃ and 50% RH. After leaving in the same atmosphere for 30 minutes, the sheet was subjected to a universal tensile compression tester according to JIS Z0237: 2009. the peel strength (N/20mm) was measured under the conditions of a drawing speed of 300 mm/min and a peel angle of 180 degrees. As the universal tensile compression tester, for example, "tensile compression tester, TG-1 kN" manufactured by Minebea Co., Ltd. If necessary, a measurement sample can be used which is prepared by attaching an appropriate resin film to the surface of the measurement object opposite to the pressure-sensitive adhesive surface, backing the resin film, and cutting the backed pressure-sensitive adhesive sheet into the above-mentioned dimensions. As the film for backing, for example, a PET film having a thickness of about 25 μm is preferably used.

In the technique disclosed herein, the thickness of the pressure-sensitive adhesive sheet is not particularly limited, and may be, for example, about 5 μm to 300 μm. From the viewpoint of thinning of the waterproof cover, the thickness of the pressure-sensitive adhesive sheet is usually suitably 200 μm or less, and may be 150 μm or less, 100 μm or less, 70 μm or less, or 40 μm or less. In some embodiments, the thickness of the pressure-sensitive adhesive sheet may be, for example, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more, from the viewpoint of processability or handleability. In the pressure-sensitive adhesive sheet without a substrate, the thickness of the pressure-sensitive adhesive layer is the thickness of the pressure-sensitive adhesive sheet.

< waterproof cover >

The waterproof cover disclosed herein can be produced by laminating an adhesive sheet on the outer peripheral edge portion of at least one surface of a waterproof film and bonding the adhesive sheet to the waterproof film with an adhesive layer included in the adhesive sheet. The method for producing the waterproof cover from the waterproof film and the adhesive sheet is not particularly limited. For example, a hole corresponding to a portion of a waterproof film effective region in a waterproof cover to be manufactured is formed in a continuous sheet-like adhesive sheet by punching or the like, and the adhesive sheet having the hole is laminated on the waterproof film. By further performing punching or the like on the laminate, a waterproof cover having a desired shape can be obtained.

The pressure-sensitive adhesive layer (film-bonding pressure-sensitive adhesive layer) bonded to the waterproof film is a pressure-sensitive adhesive layer in the case where the pressure-sensitive adhesive sheet laminated on the outer peripheral edge portion of the waterproof film is a substrate-less pressure-sensitive adhesive sheet formed of a pressure-sensitive adhesive layer, a pressure-sensitive adhesive layer in the case of a substrate-attached one-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer only on the first surface of a substrate, and a first pressure-sensitive adhesive layer in the case of a substrate-attached double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on the first surface and the second surface of a substrate. In the case of using a double-sided adhesive sheet with a substrate, the adhesive (first adhesive) constituting the first adhesive layer and the adhesive (second adhesive) constituting the second adhesive layer may be the same or different. For example, the storage modulus G' at 40 ℃ of the second adhesive may be lower than that of the first adhesive from the viewpoint of improving the adhesiveness of the waterproof cover to an adherend (e.g., a container having an opening). Specifically, the storage modulus G' at 40 ℃ of the second adhesive may be, for example, less than 53000Pa, less than 50000Pa, or less than 40000 Pa. In addition, the Tg of the base polymer of the second adhesive may also be lower than the Tg of the first adhesive. In addition, in the case where the first adhesive includes a tackifier, the second adhesive may include a tackifier in an amount greater than or different from that of the first adhesive or no tackifier in an amount less than or equal to 100 parts by weight of the base polymer of each adhesive. In addition, in the case where a crosslinking agent is used in the first binder, the same or different crosslinking agent as or from the first binder may be used in the second binder in an amount larger or smaller than that of the first binder with respect to 100 parts by weight of the base polymer of each binder, or the crosslinking agent may not be used. The thickness of the second pressure-sensitive adhesive layer may be the same as or different from the thickness of the first pressure-sensitive adhesive layer.

In the waterproof cover disclosed herein, when the adhesive sheet (first adhesive sheet) laminated on the outer peripheral edge portion of one surface of the waterproof film and the adhesive sheet (second adhesive sheet) laminated on the outer peripheral edge portion of the other surface of the waterproof film are provided, the configuration of the second adhesive sheet may be the same as or different from that of the first adhesive sheet. For example, the waterproof cover disclosed herein may be in the form of a substrate-attached adhesive sheet (single-sided adhesive sheet or double-sided adhesive sheet) as one of the first adhesive sheet and the second adhesive sheet, and a substrate-free adhesive sheet as the other. The waterproof cover of the above-described form is advantageous in terms of thinning, workability (e.g., punchability), and the like.

The dimensions of the waterproof cover disclosed herein are not particularly limited. For example, in a waterproof cover in which an adhesive sheet is laminated on the outer peripheral edge portion of a circular waterproof membrane, the diameter of the area of the waterproof membrane exposed inside the adhesive sheet (exposed area diameter) may be, for example, about 0.2mm to 50mm, about 0.2mm to 30mm, about 0.5mm to 20mm, or about 0.5mm to 15 mm. The technique disclosed herein is applied to a waterproof cover in which the waterproof film is exposed with such an exposed area diameter or a corresponding exposed area, and the effect of preventing wrinkles from occurring due to the passage of time can be exhibited appropriately. In the waterproof cover of the above-described embodiment, the outer diameter of the waterproof film may be, for example, about 2mm to 52mm, about 2mm to 32mm, about 2.5mm to 22mm, or about 2.5mm to 17 mm. The width of the adhesive layer (film bonding adhesive layer) for bonding the adhesive sheet disposed on the outer peripheral edge portion of the waterproof cover and the waterproof film may be, for example, in the range of 0.3mm to 10 mm. In some embodiments, the width of the film bonding adhesive layer may be, for example, 0.5mm or more, 0.7mm or more, 1.0mm or more, 1.2mm or more, or 1.5mm or more, from the viewpoint of enhancing the effect of preventing the occurrence of wrinkles in the waterproof film. In some embodiments, the width of the film bonding adhesive layer may be, for example, 5mm or less, 3mm or less, or 2mm or less, from the viewpoint of downsizing of the waterproof cover.

In the technique disclosed herein, a release liner may be used for the formation of an adhesive layer, the production of an adhesive sheet, the storage, distribution, shape processing, the production of a waterproof cover, the storage, distribution, and the like of a waterproof cover in the case where the waterproof cover is in a form having an exposed adhesive surface (for example, the outer surface of a base-less adhesive sheet laminated on a waterproof film or a double-sided adhesive sheet with a base). The release liner is not particularly limited, and examples thereof include a release liner having a release treatment layer on the surface of a liner base material such as a resin film or paper, and a release liner made of a low-adhesive material such as a fluorine-based polymer (polytetrafluoroethylene or the like) or a polyolefin-based resin (polyethylene, polypropylene or the like). The release treatment layer may be formed by surface-treating the backing material with a release treatment agent such as silicone, long-alkyl, fluorine, or molybdenum sulfide.

< waterproof case >

Fig. 4 shows an example of an electronic device using the waterproof cover 20 shown in fig. 3. The electronic device shown in fig. 4 is a smartphone 40. The acoustic components 32 and 34, which are an example of electronic devices, are housed inside a case (container) 52 of the smartphone 40. Typical examples of acoustic components in a smartphone are a speaker, a microphone, and a voice converter that converts an electric signal and voice. The housing 52 is provided with openings 53 and 54. The openings 53,54 are located between the sound converter and the outside. The 2 waterproof covers 20 and 20 each include a waterproof film 12 as a waterproof sound-transmitting film (for example, a porous PTFE film), and are attached to the case 52 so as to close the openings 53 and 54 by pressure-bonding the second adhesive layer 146 shown in fig. 3 around the openings 53 and 54 from the inside of the case 52. Thereby, the waterproof case 50 is constituted, and the waterproof case 50 includes: a casing 52 having openings 53 and 54, and waterproof covers 20 and 20 attached to the casing 52 so as to close the openings 53 and 54. The waterproof case 50 constitutes the smartphone 40 as an example of an audio device together with the audio components 32 and 34 housed therein. The waterproof covers 20 and 20 prevent foreign matter such as water and dust from entering the housing 52 through the openings 33 and 34, thereby protecting the sound converter. In addition, sound to and/or from the sound transducer passes through the waterproof membrane 12. The sound converter may be bonded to the waterproof cover 20 by means of a second adhesive layer 246 as shown in fig. 4. Thus, the waterproof cover 20 can be used as a fixing member for fixing the acoustic transducer to the case 52.

Examples of electronic devices are not limited to smart phones. The waterproof cover disclosed herein is applicable to communication devices such as mobile phones and smart phones, and can be applied to devices constituting tablet computers, notebook computers, computing devices (calculators and the like), electronic notebooks, electronic books, information devices for vehicles, information terminal devices such as electronic dictionaries, IC recorders, digital cameras, game devices, portable audio devices, home electric appliances with a voice guidance function, various wearable devices (e.g., wrist-worn devices such as watches, modular types that are worn on a part of the body such as clips and bands, eyeglass-type (monocular type, binocular type, and also helmet type), eyeglass-type (eyewear type), clothing-type that is attached to shirts, socks, hats, and the like in the form of accessories, ear-worn types such as earphones, and the like), portable radios, portable audio devices, and the like, Waterproof housings for various electronic devices such as portable televisions, portable printers, portable scanners, portable modems, and the like. Examples of cases in which a waterproof enclosure may be constructed using the waterproof covers disclosed herein may broadly include a package configured with a microphone; a case that houses an electronic circuit board such as an ECU (electronic Control Unit) for a vehicle and a Control board for a solar cell, a driving component such as a motor, a light source such as a vehicle lamp for an automobile, a power source such as a battery, a sensor, other electronic components, and the like; housings for household electric appliances such as electric toothbrushes and electric shavers; and the like. The waterproof cover disclosed herein is not limited to use as a component constituting an electronic device, and may be suitably used as a component of a waterproof case used for the purpose of storage, preservation, transportation, and the like of, for example, articles that are desired to be waterproof, such as clothing and paper products, and articles that are not desired to leak water to the outside, such as food, fresh food, and wet clothes.

The matters disclosed in the specification include the following.

(1) A waterproof cover is provided with:

a water-repellent film, and

an adhesive sheet laminated on the outer peripheral edge portion of the waterproof film,

the adhesive sheet comprises an adhesive layer bonded to the waterproof film,

the adhesive constituting the adhesive layer has a storage modulus G' at 40 ℃ of 53000Pa or more.

(2) The waterproof cover according to the item (1), wherein the adhesive is crosslinked with an epoxy crosslinking agent.

(3) The waterproof cover according to the above (1) or (2), wherein the adhesive is crosslinked with an isocyanate-based crosslinking agent.

(4) The waterproof cover according to any one of the above (1) to (3), wherein the adhesive has a gel fraction of 35% or more.

(5) The waterproof cover according to any one of the above (1) to (4), wherein the adhesive is an acrylic adhesive having an acrylic polymer as a base polymer.

(6) The waterproof cover according to the item (5), wherein the acrylic polymer is a polymer containing 75 wt% or more of (meth) acrylic acid C_1-4A polymer of monomeric components of an alkyl ester.

(7) The waterproof cover according to any one of the above (1) to (6), wherein the adhesive contains a tackifier.

(8) The waterproof cover according to the item (7), wherein the tackifier is one or more than two tackifier resins selected from the group consisting of a phenol-based tackifier resin, a terpene-based tackifier resin, a modified terpene-based tackifier resin, a rosin-based tackifier resin, and a hydrocarbon-based tackifier resin.

(9) The waterproof cover according to the above (7) or (8), wherein the tackifier is an acrylic oligomer having a Tg of 0 ℃ or higher.

(10) The waterproof cover according to any one of the above (7) to (9), wherein a content of the tackifier is 5 parts by weight or more and less than 40 parts by weight with respect to 100 parts by weight of the base polymer contained in the pressure-sensitive adhesive layer.

(11) The waterproof cover according to any one of the above (1) to (10), wherein the storage modulus G' of the adhesive at 80 ℃ is 20000Pa or more.

(12) The waterproof cover according to any one of the above (1) to (11), wherein the adhesive layer has a thickness of less than 25 μm.

(13) The waterproof cover according to any one of the above (1) to (12), wherein the waterproof film is formed of PTFE.

(14) The waterproof cover according to any one of the above (1) to (13), wherein the waterproof film has a thickness of 10 μm or less.

(15) The waterproof cover according to any one of the above (1) to (14), wherein the offset distance in a holding power test at 80 ℃ of the adhesive sheet is 0.4 mm/hr or less.

(16) The waterproof cover according to any one of the above (1) to (15), wherein the adhesive sheet is a double-sided adhesive substrate-attached adhesive sheet, and the adhesive sheet includes: the pressure-sensitive adhesive sheet includes a base having a first surface and a second surface, the pressure-sensitive adhesive layer being an inner pressure-sensitive adhesive layer disposed on the first surface, and an outer pressure-sensitive adhesive layer disposed on the second surface.

(17) The waterproof cover according to the item (16), wherein the base material is a resin film.

(18) The waterproof cover according to any one of the above (1) to (15), wherein the adhesive sheet is a substrate-free adhesive sheet comprising the adhesive layer.

(19) The waterproof cover according to any one of the above (1) to (18), wherein the waterproof film is exposed in an area corresponding to a circle having a diameter of 0.2mm to 50mm inside a region where the adhesive sheet is laminated.

(20) The waterproof cover according to any one of the above (1) to (19), wherein the waterproof film has a circular shape in a plan view, and an outer diameter of the waterproof film is in a range of 2mm to 52 mm.

(21) The waterproof cover according to any one of the above (1) to (20), wherein the width of the adhesive layer is 0.5mm or more and 5mm or less.

(22) The waterproof cover according to any one of the above (1) to (21), including:

the pressure-sensitive adhesive sheet as a first pressure-sensitive adhesive sheet laminated on the outer peripheral edge portion of one surface of the waterproof film, and

and a second adhesive sheet laminated on the outer peripheral edge portion of the other surface of the waterproof film.

(23) A waterproof case is provided with:

a container having an opening, and

the waterproof cover according to any one of the above (1) to (22) attached to the container so as to close the opening.

(24) An electronic device is provided with:

a container with an opening,

An electronic component accommodated in the container, and

the waterproof cover according to any one of the above (1) to (22) attached to the container so as to close the opening.

(25) The electronic device according to the above (24), wherein the electronic component is an acoustic component.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following description, "part" and "%" are based on weight unless otherwise specified.

< preparation of adhesive composition >

(adhesive composition A1)

95 parts of BA and 5 parts of AA as monomer components, 0.2 part of AIBN as a polymerization initiator, and ethyl acetate as a polymerization solvent were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel, and fed at 60 ℃ under a nitrogen streamSolution polymerization was carried out for 8 hours to obtain a solution of an acrylic polymer. The acrylic polymer has a Mw of about 60X 10⁴。

To the acrylic polymer solution, 25 parts of acrylic oligomer as a tackifier, 1 part of an isocyanate-based crosslinking agent (trade name "CORONATE L", a 75% ethyl acetate solution of a trimethylolpropane/tolylene diisocyanate trimer adduct, manufactured by tokyo co., ltd.) and 0.075 part of an epoxy-based crosslinking agent (trade name "tetra-C", 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, manufactured by mitsubishi gas chemical corporation) were added and mixed with stirring, based on 100 parts of the acrylic polymer contained in the solution, to prepare an adhesive composition a 1.

As the acrylic oligomer, those prepared by the following methods were used. Specifically, 95 parts and 5 parts of CHMA, 10 parts of AIBN as a polymerization initiator, and toluene as a polymerization solvent were put into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux condenser, and a dropping funnel, and solution polymerization was carried out at 85 ℃ for 5 hours under a nitrogen flow to obtain an acrylic oligomer having Mw of about 3600.

(adhesive composition A2)

In the preparation of adhesive composition A1, 30 parts of a terpene-phenol resin (trade name "YS Polyster S-145", Yasuhara Chemical Co., LTD, softening point: about 145 ℃, hydroxyl value: 70 to 110mgKOH/g) was used instead of the acrylic oligomer, and the amounts of the isocyanate-based crosslinking agent and the epoxy-based crosslinking agent were changed to 2 parts and 0.01 part, respectively. Otherwise, adhesive composition a2 was prepared in the same manner as in the preparation of adhesive composition a 1.

(adhesive composition A3)

In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux condenser and a dropping funnel, 70 parts of BA, 30 parts of 2EHA, 3 parts of AA, 0.05 part of 4-hydroxybutyl acrylate (4HBA), 0.35 part of AIBN as a polymerization initiator and ethyl acetate as a polymerization solvent were charged as monomer components, and solution polymerization was carried out at 65 ℃ for 3.5 hours in a nitrogen stream to obtain a solution of an acrylic polymer.

To the acrylic polymer solution, 30 parts of polymerized rosin ester (trade name "Pensel D125", manufactured by Mitsui chemical industries, Ltd., softening point 125 ℃) and 2 parts of isocyanate-based crosslinking agent (trade name "TAKENATE L", manufactured by Mitsui chemical Co., Ltd.) were added and mixed with stirring, based on 100 parts of the acrylic polymer contained in the solution, to prepare a pressure-sensitive adhesive composition A3 a.

Adhesive composition A3b was prepared in the same manner as in the preparation of adhesive composition A3a, except that the amount of the isocyanate-based crosslinking agent used was changed to 3 parts.

(adhesive composition A4)

100 parts of BA, 5 parts of vinyl acetate (VAc), 3 parts of AA, 0.1 part of 2-hydroxyethyl acrylate (HEA), 0.3 part of AIBN as a polymerization initiator and toluene as a polymerization solvent were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux condenser and a dropping funnel, and solution polymerization was carried out at 60 ℃ for 6 hours to obtain a solution of an acrylic polymer. The Mw of the acrylic polymer was 55X 10⁴。

To the acrylic polymer solution, 40 parts of a tackifier resin and 2 parts of an isocyanate crosslinking agent (trade name "CORONATE L", manufactured by tokyo co., ltd.) were added to 100 parts of the acrylic polymer contained in the solution, and the mixture was stirred and mixed to prepare an adhesive composition a 4.

As the tackifier resin, 10 parts of polymerized rosin ester (trade name "HARITACK PCJ", manufactured by Harima Chemicals Group, Inc.) having a softening point of about 125 ℃, 10 parts of stabilized rosin ester (trade name "HARITACK SE 10", manufactured by Harima Chemicals Group, Inc.) having a softening point of about 80 ℃,5 parts of hydrogenated rosin methyl ester (trade name "M-HDR", manufactured by Ringzhi chemical Co., Ltd., Guangxi province, liquid), and 15 parts of terpene phenol resin (trade name "SUMILIESIN PR-12603", SuTERomo Bakelite Co., Ltd.) having a softening point of about 133 ℃ were used.

(adhesive composition A5)

Comprises a stirrer, a thermometer, and nitrogen gas introductionIn a reaction vessel including a tube, a reflux condenser and a dropping funnel, 2 parts of EHA 90 and 10 parts of AA as monomer components and 199 parts of ethyl acetate as a polymerization solvent were charged, and the mixture was stirred for 2 hours while introducing nitrogen gas. After removing oxygen from the polymerization system in this manner, 0.2 part of benzoyl peroxide as a polymerization initiator was added and solution polymerization was carried out at 60 ℃ for 6 hours to obtain a solution of an acrylic polymer. The acrylic polymer has a Mw of about 120X 10⁴。

To the acrylic polymer solution, 0.175 part of an epoxy crosslinking agent (trade name "TETRAD-C", 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, manufactured by mitsubishi gas chemical corporation) was added per 100 parts of the acrylic polymer contained in the solution, followed by mixing with stirring to prepare an adhesive composition a 5.

(adhesive composition A6)

In the preparation of adhesive composition a5, the amount of epoxy crosslinking agent used was changed to 0.05 parts, and 20 parts of terpene-phenol resin (trade name "YS polymer S-145", Yasuhara Chemical co., LTD, softening point about 145 ℃, hydroxyl value 70 to 110mgKOH/g) was added to 100 parts of acrylic polymer contained in the acrylic polymer solution, and adhesive composition a6 was prepared in the same manner as in the preparation of adhesive composition a 5.

< preparation of Water-repellent film >

In a PTFE dispersion (concentration of PTFE powder: 40% by weight, average particle diameter of PTFE powder: 0.2 μm, and nonionic surfactant: 6 parts per 100 parts of PTFE), 1 part of a fluorine-based surfactant (MEGAFACE F-142D, manufactured by DIC) was added to 100 parts of PTFE contained in the dispersion. Subsequently, a long polyimide film (thickness 125 μm) was immersed in the PTFE dispersion and pulled out, thereby forming a coating film of the PTFE dispersion on the film. At this time, the thickness of the coating film was set to 20 μm by a measuring bar. Next, the above-described coating film was heated at 100 ℃ for 1 minute, followed by heating at 390 ℃ for 1 minute, whereby water contained in the above-described dispersion was evaporated and removed, and the remaining PTFE particles were bonded to each other, to obtain a PTFE film. The above immersion and heating were further repeated 2 times, and then the obtained PTFE film (thickness 25 μm) was peeled off from the polyimide film.

The PTFE film obtained in the above was rolled in the MD direction at a rolling magnification of 2.5 times using a roll rolling device. The set temperature of the rolls in the roll rolling device was set to 170 ℃. Next, the above-described rolled PTFE film was stretched at a stretching ratio of 2 times in the TD direction by a tenter. The stretching temperature was set at 170 ℃. Thus, a thickness of 8 μm and an area density of 13.0g/m were obtained²And a PTFE porous membrane having an air permeability of 68 seconds/100 mL. In the production of a waterproof cover described later, the PTFE porous film is used as a waterproof film.

< preparation of pressure-sensitive adhesive sheet >

(adhesive sheet S1)

2 commercially available release liners each comprising a polyester film having one surface subjected to a release treatment were prepared. The pressure-sensitive adhesive composition A1 was applied to the release surface of each release liner and dried at 100 ℃ for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 13 μm. The adhesive layers on the release liners were bonded to the first and second surfaces of a polyethylene terephthalate (PET) film having a thickness of 4 μm as a substrate, thereby producing a double-sided adhesive sheet with a substrate S1 having an adhesive layer on the first and second surfaces of the PET film and a total thickness of 30 μm. The first adhesive surface and the second adhesive surface of the adhesive sheet were protected by the 2-sheet release liner.

(adhesive sheets S2-S9)

Adhesive sheets S2 to S9 were produced in the same manner as in the production of the adhesive sheet S1, except that the type of adhesive composition used, the type and thickness of the substrate, and the thickness of the adhesive layer were changed as shown in table 2. Was used for production of the adhesive sheet S9. As the pressure-sensitive adhesive sheets S2 to S8, PET films having thicknesses shown in table 2 were used as substrates. As the pressure-sensitive adhesive sheet S9, a black polyethylene foam sheet (expansion ratio 3 times) having a thickness shown in table 2 was used as a substrate.

(adhesive sheet S10)

2 commercially available release liners each comprising a polyester film having one surface subjected to a release treatment were prepared. The release surface of each release liner of the 1 st sheet was coated with the adhesive composition A5 and dried at 100 ℃ for 2 minutes to form an adhesive layer having a thickness of 50 μm. The 2 nd release liner was attached to the surface of the adhesive layer. In this manner, a substrate-free psa sheet S10 formed of the psa layer was obtained. Both surfaces of the pressure-sensitive adhesive layer in this pressure-sensitive adhesive sheet S10 were protected by the 2-sheet release liner.

(adhesive sheet S11)

2 commercially available release liners each comprising a polyester film having one surface subjected to a release treatment were prepared. The pressure-sensitive adhesive composition A6 was applied to the release surface of each release liner and dried at 100 ℃ for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 25 μm. The adhesive layers on the release liners were bonded to the first and second surfaces of a Polyimide (PI) film having a thickness of 50 μm as a substrate, to prepare a double-sided adhesive sheet with a substrate S11 having an adhesive layer on the first and second surfaces of a PET film and a total thickness of 100 μm. The first adhesive surface and the second adhesive surface of the adhesive sheet were protected by the 2-sheet release liner.

< production of waterproof cover >

Using the waterproof film and the pressure-sensitive adhesive sheets S1 to S11, 50 waterproof cover samples (sample number N is 50) were prepared for examples 1 to 11, respectively. Specifically, 2 adhesive sheets S1 to S11 were prepared, and 50 holes (5 × 10 rows) having a diameter of 2.5mm were punched out at regular intervals in each adhesive sheet, and then the first adhesive surface was bonded to the first surface and the second surface of the waterproof film, and the outer periphery was punched out, thereby producing a waterproof cover sample 60 having a configuration in which annular adhesive sheets 14 and 24 having an outer diameter of 6.0mm and an inner diameter of 2.5mm were laminated on the outer peripheral edge portions of the first surface 12A and the second surface 12B of a circular waterproof film 12 having a diameter of 6.0mm as shown in fig. 5. Each sample 60 has the same configuration as the waterproof cover 20 shown in fig. 3. One adhesive side 60A of each of the 50 samples 60 is collectively protected by a release liner 62. The other adhesive surface 60B of sample 60 was protected by a release liner 64 having the same shape (ring shape) as that of the adhesive sheets 14 and 24, respectively. Inside the inner diameter of the adhesive sheets 14 and 24, the waterproof film 12 is exposed in a circular shape having a diameter of 2.5 mm. Immediately after the waterproof cover samples of examples 1 to 11 were produced, the number of samples in which wrinkles were observed in the waterproof film was 0 in each of 50 waterproof cover samples.

< measurement and evaluation >

(storage modulus G')

The storage modulus G 'at 40 ℃ and the storage modulus G' at 80 ℃ of the adhesive formed from each adhesive composition were measured by the methods described above. The results are shown in Table 1.

(gel fraction)

The gel fraction of the adhesive formed from each adhesive composition was measured by the method described above. As a result, the gel fraction of the adhesives formed from the adhesive compositions a1, a2, and a6 was 40% or more (50 to 60%), and the gel fraction of the adhesive formed from the adhesive composition a5 was about 80%. The gel fraction of the adhesives formed from adhesive compositions A3a, A3b, and a4 was not more than 35%.

(Retention force test)

The adhesive sheets S1 to S11 were subjected to retention tests at 40 ℃ and 80 ℃.

[80 ℃ Retention test ]

A PET film having a thickness of 50 μm was attached to the second adhesive surface of the adhesive sheet in an atmosphere of 23 ℃ and 50% RH, and the adhesive sheet was backed up and cut into a width of 10mm to prepare a measurement sample. The first adhesive surface of the measurement sample was attached to a phenol resin plate as an adherend with an adhesive area of 10mm in width and 20mm in length by reciprocating a 2kg roller once. The measurement sample attached to the adherend was allowed to hang down in an environment of 80 ℃ and left standing for 30 minutes, and then a load of 500g was applied to the free end of the measurement sample. The measurement sample after being left at 80 ℃ for 1 hour in the state where the load was applied was measured for the offset distance (mm) from the first sticking position. The adhesive sheets of the respective examples were tested using 3 measurement samples (i.e., N is 3), and the arithmetic average of the offset distances thereof is shown in table 1.

[40 ℃ Retention test ]

The 40 ℃ holding force test was performed in the same manner as the 80 ℃ holding force test except that the temperature of the environment in which the measurement sample was suspended and the environment in which the measurement sample was left for 1 hour with a load of 500g was changed to 40 ℃. The adhesive sheets of the respective examples were tested using 3 measurement samples (i.e., N is 3), and the arithmetic average of the offset distances thereof is shown in table 1.

(presence or absence of occurrence of wrinkles)

After the waterproof cover samples of the respective examples were kept in an environment of 23 ℃ and 50% RH for 3 days, whether or not wrinkles were observed in the waterproof film exposed on the inner side of the inner diameter of the adhesive sheet was judged by visual observation of the waterproof cover samples. As a result, in each of the 50 waterproof cover samples, when only 1 waterproof cover sample was observed, the occurrence of wrinkles was evaluated as "present", and when no wrinkles were observed, the occurrence of wrinkles was evaluated as "absent". The results are shown in Table 1.

(measurement of peel Strength of PTFE)

A PET film having a thickness of 25 μm was attached to the second adhesive surface of the adhesive sheets S2, S4 and S7 and backed up in a measuring atmosphere at 23 ℃ and 50% RH, and cut into a size of 20mm in width and 100mm in length to prepare a measurement sample. The first adhesive surface of the measurement sample was subjected to the measurement of the peel strength (N/20mm) to PTFE by the above-described method using the waterproof film produced above as an adherend. As a result, it was confirmed that the peel strength of the pressure-sensitive adhesive sheet S2 against PTFE was 4.4N/20mm, the peel strength of the pressure-sensitive adhesive sheet S4 was 4.8N/20mm, and the peel strength of the pressure-sensitive adhesive sheet S7 was 6.3N/20mm, which were all 2.0N/20mm or more.

[ Table 1]

As shown in table 1, the waterproof covers of examples 1 to 5, 10 and 11, in which the storage modulus G' at 40 ℃ of the adhesive for bonding the adhesive sheet to the waterproof film was 53000Pa or more (i.e., 53.0kPa or more), suppressed the generation of wrinkles in the waterproof film caused by the passage of time as compared with the waterproof covers of examples 6 to 9.

Specific examples of the present invention have been described above in detail, but these are merely examples and do not limit the claims. The techniques described in the claims include those in which various modifications and changes are made to the specific examples illustrated above.

Description of the reference numerals

10. 20: waterproof cover

12: waterproof film

12A: a surface

12B: the other surface

14. 24: adhesive sheet

32,34: sound component

40: intelligent telephone (electronic equipment)

50: waterproof case

52: casing (Container)

53,54: opening of the container

60: waterproof cover sample

62. 64: release liner

142. 242: base material

142A, 242A: first side (side surface of waterproof film)

142B, 242B: second surface (outer surface)

144. 244: first adhesive layer (inner adhesive layer, film bonding adhesive layer)

146. 246: second adhesive layer (outer adhesive layer)