Adherend with adhesive layer, roll-shaped adherend with adhesive layer, and structure

Abstract

To provide an adherend with an adhesive layer which has good storage stability of an uncured curable resin composition and can suppress stickiness of the adhesive layer, a roll-shaped adherend with an adhesive layer using the adherend with an adhesive layer, and a structure using the adherend with an adhesive layer.SOLUTION: The adherend with an adhesive layer has an adherend made of a metal material or a resin material, and an adhesive layer laminated on the surface of the adherend and formed of an uncured curable resin composition in a solid state at room temperature. The curable resin composition contains (A) a crystalline epoxy resin having a melting point of 90 °C or higher and (B) a curing agent that is solid at 25 °C. The curable resin composition preferably further contains an amorphous thermoplastic resin (C). The adhesive layer-attached roll-shaped adherend is configured in a roll shape by winding the adhesive layer-attached adherend in the longitudinal direction. The structure is constituted by using an adherend with an adhesive layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adherend with an adhesive layer, a roll-shaped adherend with an adhesive layer, and a structure. [Background technology]

[0002] BACKGROUND ART Conventionally, adherends with an adhesive layer have been known, in which the surface of an adherend made of various metal materials or resin materials is precoated with an adhesive layer made of an adhesive resin composition.

[0003] For example, Patent Document 1 describes an adherend with an adhesive layer, which is formed by applying a liquid epoxy adhesive resin composition to one side of an aluminum-based material as an adherend, and then drying the composition at 150°C to cause a curing reaction, resulting in an adhesive layer that is semi-cured and tack-free.

[0004] Furthermore, Patent Document 2 describes a sheet-like resin composition that is not an adherend with an adhesive layer, but is used to insert into gaps in an adherend and adhere it, and contains a crystalline bisphenol F type epoxy resin with a melting point of 70°C or more and 90°C or less, a solid multifunctional epoxy resin with a softening point of 75°C or less, etc. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-104300 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-113483 Summary of the Invention [Problem to be solved by the invention]

[0006] In the production of the above-mentioned adherend with an adhesive layer, the resin composition may be stored for a long period of time until the adhesive layer is formed. If the viscosity of the resin composition in a liquid state increases after storage compared to when the resin composition was first prepared, this will cause problems in the production of the adherend with an adhesive layer. Therefore, the resin composition is required to have good storage stability.

[0007] Furthermore, if the adhesive layer surface is sticky, it becomes difficult to handle the adherend with the adhesive layer. Therefore, a release film is generally provided on the adhesive layer surface to prevent the sticky adhesive layer from sticking to other objects. Even if the adhesive layer surface can be prevented from becoming sticky at room temperature, it often becomes sticky when exposed to high temperatures of around 80°C.

[0008] When the adherends with adhesive layers of Patent Document 1 are heated to about 80° C., the adhesive layers soften and the adherends with adhesive layers stick together. Furthermore, the adherends with adhesive layers of Patent Document 1 must be semi-cured before bonding to the other adherend in order to make the adhesive layer tack-free, which reduces the curing reaction during bonding and reduces adhesion.

[0009] The sheet-shaped resin composition of Patent Document 2 uses a crystalline bisphenol F epoxy resin with a melting point of 70° C. or higher and 90° C. or lower, but also uses a solid multifunctional epoxy resin with a softening point of 75° C. or lower, which lowers the overall melting point. Therefore, when the sheet-shaped resin composition of Patent Document 2 is exposed to a high temperature of about 80° C., the adhesive layer surface becomes sticky, causing adhesion between adherends with the adhesive layer.

[0010] The present invention has been made in view of the above problems, and aims to provide an adherend with an adhesive layer in which the storage stability of the uncured curable resin composition is good and the stickiness of the adhesive layer can be suppressed, an adherend with an adhesive layer roll using the adherend with an adhesive layer, and a structure using the adherend with an adhesive layer. [Means for solving the problem]

[0011] One aspect of the present invention is an adherend made of a metal material or a resin material; an adhesive layer laminated on the surface of the adherend and formed from an uncured curable resin composition in a solid state at room temperature; The curable resin composition comprises (A) a crystalline epoxy resin having a melting point of 90°C or higher; (B) a curing agent that is solid at 25°C; It is on an adherend with an adhesive layer.

[0012] Another aspect of the present invention is The adherend with the adhesive layer is a roll-shaped adherend with the adhesive layer that is wound in the longitudinal direction and configured into a roll shape.

[0013] Yet another aspect of the present invention is a method for producing a semiconductor device comprising: The present invention relates to a structure constructed using the adherend with the adhesive layer. [Effects of the Invention]

[0014] The adherend with the adhesive layer has the above-described configuration, and therefore the uncured curable resin composition in the adherend with the adhesive layer has good storage stability, and the adhesive layer can be prevented from becoming tacky.

[0015] The roll-shaped adherend with an adhesive layer has the above-mentioned configuration. Therefore, the roll-shaped adherend with an adhesive layer can be supplied to a highly productive roll-to-roll line, making it possible to manufacture structures at low cost. Furthermore, the roll-shaped adherend with an adhesive layer can be formed into adherends with adhesive layers of various dimensions by appropriately selecting the cutting position in the longitudinal direction, making it possible to apply the adherend with an adhesive layer to structures of various dimensions, thereby providing a high degree of freedom in production.

[0016] The structure is constructed using the adherend with the adhesive layer, which can suppress stickiness of the adhesive layer. Therefore, the structure has excellent workability when handling the adherend with the adhesive layer during production. Furthermore, the structure can be bonded to a counterpart adherend by heating the adherend with the adhesive layer during production, so the step of applying a separate adhesive when bonding the adherends can be omitted. Therefore, the structure has excellent productivity. DETAILED DESCRIPTION OF THE INVENTION

[0017] The adherend with an adhesive layer, the roll-shaped adherend with an adhesive layer, and the structure of this embodiment will be described in detail below. Note that the adherend with an adhesive layer, the roll-shaped adherend with an adhesive layer, and the structure of this embodiment are not limited to the following examples. Furthermore, the lower and upper limits of the numerical ranges shown below can be combined arbitrarily (omitted below).

[0018] (Embodiment 1) A description will now be given of an adherend with an adhesive layer of embodiment 1. The adherend with an adhesive layer of this embodiment has an adherend and an adhesive layer formed from an uncured curable resin composition.

[0019] The adherend is made of a metal material or a resin material. Examples of metal materials that make up the adherend include aluminum, aluminum alloys, copper, copper alloys, iron, iron alloys, nickel, nickel alloys, magnesium, magnesium alloys, titanium, and titanium alloys. Metal materials can be selected according to the application and purpose, taking into consideration lightness, thermal conductivity, strength, and the like.

[0020] For example, heat exchangers, such as automobile radiators, are primarily manufactured by NB brazing aluminum and aluminum alloys. However, from the perspective of a circular economy, future manufacturing using recycled aluminum is necessary. However, recycled aluminum often contains magnesium as an impurity, making NB brazing difficult for aluminum and aluminum alloys containing magnesium. Therefore, when bonding such adherends, an alternative bonding technique to brazing is needed. One alternative bonding technique to brazing is to form a pre-adhesive layer on the adherend by applying a thermoplastic resin to the surface of the adherend and allowing it to harden. However, the higher the temperature, the more tacky this adhesive layer becomes, making it more susceptible to sticking. Furthermore, since the adhesive layer after bonding is simply formed by melting and hardening the thermoplastic resin and not curing by crosslinking, it becomes prone to peeling at temperatures around 150°C, for example. In contrast, the adhesive layer of the adherend with an adhesive layer of this embodiment is formed from an uncured curable resin composition, so the cured adhesive layer does not melt and peel at temperatures around 150°C. Therefore, in the adherend with adhesive layer of this embodiment, even if the adherend is composed of aluminum or an aluminum alloy containing Mg element, the adhesive layer surface becomes less sticky at high temperatures and adhesive strength can be ensured.

[0021] Examples of resin materials constituting the adherend include polyesters such as polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyamide (PA), polycarbonate (PC), polyacetal (POM), and polyether ether ketone (PEEK). Engineering plastics such as polybutylene terephthalate and polyphenylene sulfide can be selected as the resin material constituting the adherend from the viewpoints of ease of moldability and excellent strength of the structure when used in a structure. As long as at least the portion of the adherend where the adhesive layer is formed (the portion in contact with the adhesive layer) is made of the above-mentioned material, the portions other than the portion where the adhesive layer is formed may be made of the same material as the portion where the adhesive layer is formed, or may be made of a different material. The shape of the adherend can be appropriately selected depending on the application of the adherend with the adhesive layer. Examples of the shape of the adherend include a plate-like shape and a plate-like shape that has been given a predetermined shape.

[0022] The adhesive layer is formed from an uncured curable resin composition. Therefore, the adherend with the adhesive layer can be adhered to a counter adherend via the adhesive layer by curing the curable resin composition. The adhesive layer is laminated on the surface of the adherend. The adhesive layer may be formed on the entire surface of the adherend, or may be formed on only a portion of the surface of the adherend. For example, when the adherend is plate-shaped, the adhesive layer can be formed on at least one surface of the plate-shaped adherend, or may be formed on one or both surfaces of the plate-shaped adherend.

[0023] An uncured curable resin composition is in a solid state at room temperature. In other words, an uncured curable resin composition is solid at room temperature. In the adherend with an adhesive layer of this embodiment, "uncured" includes not only a completely uncured state but also a semi-cured state such as a B-stage state. Although the curable resin composition forming the adhesive layer of the adherend with an adhesive layer of this embodiment may be in a semi-cured state, the need for semi-curing is low because the curable resin composition is in a solid state at room temperature and has almost no tack (stickiness) or stickiness. Rather, it is preferable that the curable resin composition be in a state where the curing reaction has not progressed, i.e., a curing reaction rate of 0%, from the viewpoint that the entire curable resin composition can be used in the curing reaction, which is advantageous for improving adhesive strength. The curing reaction rate can be determined by differential scanning calorimetry (DSC).

[0024] The thickness of the adhesive layer is not particularly limited, but can be, for example, 10 μm to 5 mm, from the viewpoints of wettability and spreadability over the uneven surface of the adherend and prevention of contamination of the surrounding area by excess adhesive.

[0025] Here, the above-mentioned curable resin composition contains (A) a crystalline epoxy resin and (B) a curing agent as essential components.

[0026] The crystalline epoxy resin of component (A) has a melting point of 90°C or higher. If the melting point is less than 90°C, the adhesive layer surface will become sticky when exposed to a high-temperature environment of 80°C (for example, during transportation by truck in summer or during storage), making it more likely to stick to the opposing adherend.

[0027] The melting point of the crystalline epoxy resin is preferably 93° C. or higher, more preferably 95° C. or higher, and even more preferably 100° C. or higher. The melting point of the crystalline epoxy resin can be set to, for example, 200° C. or lower, from the viewpoint of suppressing the curing temperature.

[0028] Examples of crystalline epoxy resins include biphenyl-type epoxy resins, dioxane-type epoxy resins, and anthracene-type epoxy resins. A representative example of a biphenyl-type epoxy resin is YX4000 manufactured by Mitsubishi Chemical Corporation. A representative example of a dioxane-type epoxy resin is YDC1312 manufactured by Nippon Steel Chemical & Material Co., Ltd. A representative example of anthracene-type epoxy resin is YX8800 manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

[0029] The crystalline epoxy resin may or may not contain an epoxy resin having a substituted biphenyl skeleton. The crystalline epoxy resin may or may not contain an epoxy resin having an unsubstituted biphenyl skeleton. Preferably, the mass ratio of the epoxy resin having an unsubstituted biphenyl skeleton in the crystalline epoxy resin is 2% or more and 60% or less. Hereinafter, the "mass ratio of the epoxy resin having an unsubstituted biphenyl skeleton in the crystalline epoxy resin" may be simply abbreviated as the "unsubstituted biphenyl epoxy ratio."

[0030] When the unsubstituted biphenyl epoxy ratio is within the above range, the liquid curable resin composition tends to convert more quickly into a solid film when it returns to a solid curable resin composition. This has the advantage of improving the efficiency of the application process of the curable resin composition to the adherend. This is thought to be because there is less interference due to substituents between adjacent epoxy resins. That is, adjacent epoxy resins tend to aggregate and align more easily, which is thought to increase the crystallization rate of the epoxy resin. Furthermore, the cohesive strength between epoxy resins is thought to increase, which is advantageous for improving the adhesive strength after curing.

[0031] The unsubstituted biphenyl epoxy ratio is preferably 4% or more, more preferably 6% or more, even more preferably 8% or more, and even more preferably 10% or more, and is preferably 59% or less, more preferably 58% or less, and even more preferably 55% or less.

[0032] The curing agent (B) is capable of reacting with the crystalline epoxy resin (A). However, the curing agent (B) is a solid at 25°C. If the curing agent is liquid at 25°C, the storage stability of the uncured curable resin composition will be poor, and the adhesive layer surface will become sticky when exposed to a high-temperature environment of 80°C.

[0033] Examples of curing agents include amine-based curing agents. Specific examples of curing agents include dicyandiamide (DICY) or its derivatives, diaminodiphenyl sulfone (DDS) or its derivatives, and aromatic diamines such as 4,4-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4-aminophenyl 4-aminobenzoate, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminobenzanilide, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, or 2,2'-bis(3-amino-4-hydrophenyl)propane, or their derivatives. A representative example of dicyandiamide or its derivatives is DICY7 manufactured by Mitsubishi Chemical Corporation. These can be used alone or in combination of two or more.

[0034] As the curing agent, an amine-based curing agent having a melting point of 170°C or higher can be suitably used. A curing agent having a melting point of 170°C or higher is preferable because it is less likely to cause stickiness on the adhesive layer surface when exposed to a high-temperature environment of 80°C, and also because it is less likely to cause a curing reaction when the curable resin composition is heated to about 130°C and liquefied during application. The melting point of the curing agent can be preferably 180°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher. The melting point of the curing agent can be preferably 300°C or lower, more preferably 280°C or lower.

[0035] Furthermore, since the curing agent is an amine-based agent, it has high reactivity with epoxy groups, which shortens the time required for adhesive strength to develop through crosslinking, thereby providing the advantage of shortening the manufacturing time.

[0036] The mass ratio of the curing agent to the crystalline epoxy resin, expressed as the equivalent of active hydrogen to epoxy group, can be preferably 0.2 to 2.0 equivalents, more preferably 0.3 to 1.8 equivalents, and even more preferably 0.4 to 1.5 equivalents. In this case, the storage stability of the uncured curable resin composition is excellent, and the strength of the adhesive layer after curing is also excellent.

[0037] In the adherend with the adhesive layer of this embodiment, the curable resin composition may further contain (C) an amorphous thermoplastic resin. In this case, higher adhesive strength is more easily ensured. In addition, the flexibility of the adhesive layer after curing is increased, which is also advantageous for improving toughness.

[0038] From the viewpoint of strength, toughness, etc. at high temperatures, the amorphous thermoplastic resin preferably has a glass transition temperature of 150° C. or higher, more preferably 180° C. or higher, and even more preferably 200° C. or higher. Furthermore, it is preferable that the amorphous thermoplastic resin is compatible with the crystalline epoxy resin before the crystalline epoxy resin is crosslinked.

[0039] Furthermore, the amorphous thermoplastic resin is preferably contained in the curable resin composition as particles. Since the amorphous thermoplastic resin is a polymer, if it is present in a uniformly dissolved state in the uncured curable resin composition, when the uncured curable resin composition in a liquid state is applied to the adherend during the production of an adherend with an adhesive layer, the viscosity of the curable resin composition increases, and coating workability decreases. In contrast, when the amorphous thermoplastic resin is contained in the curable resin composition as particles, the viscosity of the curable resin composition is less likely to increase, and coating workability is improved. In this case, all of the amorphous thermoplastic resin contained in the curable resin composition may be present as particles, or a portion of the amorphous thermoplastic resin contained in the curable resin composition may be present as particles, with the remaining amorphous thermoplastic resin dissolved in the curable resin composition. In order to make the amorphous thermoplastic resin exist as particles in the curable resin composition, for example, the heating time when the crystalline epoxy resin and the amorphous thermoplastic resin described below are heated and stirred to make them compatible may be set shorter than the heating time required for the amorphous thermoplastic resin to completely dissolve, so that some of the amorphous thermoplastic resin remains undissolved. Alternatively, the heated and melted crystalline epoxy resin may be simply mixed with the particulate amorphous thermoplastic resin.

[0040] The average particle size of the amorphous thermoplastic resin particles in the curable resin composition can be preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.5 μm or more, from the viewpoints of improving adhesive strength and toughness of the adhesive layer after curing. Furthermore, the average particle size of the amorphous thermoplastic resin particles can be preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less, from the viewpoints of uniform dispersibility in the curable resin composition, the properties of the curable resin composition, and suppression of unevenness on the adhesive layer surface. The average particle size is the particle size (diameter) d50 at which the volume-based cumulative frequency distribution measured by laser diffraction / scattering method shows 50%.

[0041] Specific examples of amorphous thermoplastic resins include polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), modified polyphenylene ether (m-PPE), polyethersulfone (PES), polyetherimide (PEI), polyamideimide (PAI), and polyphenylene ether (PPE). These can be used alone or in combination of two or more. Of these, polyethersulfone is preferred from the viewpoints of compatibility with crystalline epoxy resins, high glass transition temperature, and the like.

[0042] When the curable resin composition contains (C) an amorphous thermoplastic resin, the mass ratio of the amorphous thermoplastic resin to the crystalline epoxy resin is preferably 5% or more and 100% or less. In this case, the storage stability of the uncured curable resin composition and the adhesive strength of the adhesive layer after curing can be improved while suppressing stickiness of the adhesive layer. From the viewpoint of improving the toughness of the adhesive layer, the mass ratio of the amorphous thermoplastic resin to the crystalline epoxy resin can be preferably 6% or more and 80% or less, more preferably 7% or more and 70% or less, and even more preferably 8% or more and 60% or less.

[0043] The curable resin composition described above may contain, in addition to the above components, for example, a curing accelerator. From the viewpoint of the storage stability of the uncured curable resin composition, the curing accelerator preferably has a melting point of 130°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. From the viewpoint of preventing the reaction initiation temperature from becoming too high, the curing accelerator preferably has a compatibilization temperature with the crystalline epoxy resin or curing agent of 200°C or lower, more preferably 170°C or lower, and even more preferably 150°C or lower.

[0044] When the curable resin composition contains a curing accelerator, the mass ratio of the curing accelerator to the crystalline epoxy resin can be 0.01% or more and 5% or less, which can improve the storage stability of the uncured curable resin composition and suppress stickiness of the adhesive layer, while shortening the curing time and accelerating the development of adhesive strength.

[0045] According to the adherend with an adhesive layer of this embodiment, the storage stability of the uncured curable resin composition is good, and an adherend with an adhesive layer can be obtained that can suppress stickiness of the adhesive layer.

[0046] Furthermore, the adhesive layer-attached adherend of this embodiment has a solid adhesive layer at room temperature (25°C) before curing, and the adhesive layer surface is less tacky, resulting in excellent workability during handling. Furthermore, when multiple adhesive layer-attached adherends are stacked and transported or stored without a release film, even when heated to approximately 80°C, the adhesive layer surface remains non-tacky, preventing the adhesive layer-attached adherends from sticking to each other. Furthermore, at a temperature at which at least the crystalline epoxy resin of component (A) liquefies (a temperature at least equal to or higher than the melting point of the crystalline epoxy resin of component (A)), for example, approximately 120°C to 130°C, the adhesive layer melts, crosslinks, and hardens, ensuring adhesive strength between the adhesive layer and the opposing adherend. The adhesive layer-attached adherend of this embodiment remains solid at room temperature and exhibits reduced tackiness, even when the curing reaction rate of the adhesive layer is 0%. Therefore, the adherend with an adhesive layer of this embodiment increases the curing reaction that contributes to adhesion, which is advantageous for improving adhesion, compared to techniques that aim to reduce tackiness by putting the adhesive layer into a B-stage state, i.e., by slightly accelerating the curing reaction of the adhesive layer.

[0047] Furthermore, since the adhesive layer-attached adherend of this embodiment has the adhesive layer pre-coated on the surface of the adherend, it can be adhered to a mating adherend by heating the adhesive layer-attached adherend. Therefore, the adhesive layer-attached adherend of this embodiment can omit the step of separately applying an adhesive when adhering adherends during the production of a structure. The adhesive layer-attached adherend of this embodiment can improve the productivity of structures.

[0048] The adherend with the adhesive layer of this embodiment can be produced, for example, as follows, but is not limited to this.

[0049] An uncured curable resin composition that is in a solid state at room temperature is prepared. The curable resin composition can be prepared, for example, by kneading the various components simultaneously at a temperature of about 80°C to 100°C and then returning the mixture to a temperature at which the components become solid, such as room temperature. Alternatively, when using an amorphous thermoplastic resin (C), the composition can be prepared as follows: The crystalline epoxy resin (A) and the amorphous thermoplastic resin (C) are heated and stirred at a temperature at which at least the crystalline epoxy resin (A) becomes liquefied (a temperature at least equal to or higher than the melting point of the crystalline epoxy resin (A)) to dissolve or disperse the components, and then the mixture is returned to a temperature below the melting point, such as room temperature, to form a solid solution or dispersion. This solid solution or dispersion is then pulverized to form a pulverized product. This pulverized product is then kneaded with the curing agent (B), and, if necessary, a curing accelerator, at a temperature of about 80°C to 100°C, and the mixture is returned to a temperature at which the components become solid, such as room temperature. This allows the preparation of a curable resin composition.

[0050] Next, the uncured curable resin composition in a solid state at room temperature is heated to a temperature at which the curable resin composition liquefies, liquefied, applied to the surface of the adherend, and then returned to a temperature at which the curable resin composition becomes solid. The uncured curable resin composition in a solid state can also be placed on the surface of the adherend that has been heated to a temperature at which the curable resin composition liquefies, and the curable resin composition can be liquefied and applied. After the uncured curable resin composition in a solid state is placed on the surface of the adherend, the adherend or the entire body can be heated to a temperature at which the curable resin composition liquefies.

[0051] In this manner, the adherend with the adhesive layer of this embodiment can be produced.

[0052] (Embodiment 2) A roll-shaped adherend with an adhesive layer of embodiment 2 will now be described. The roll-shaped adherend with an adhesive layer of this embodiment is configured into a roll by longitudinally winding the adherend with an adhesive layer of embodiment 1. Specifically, the roll-shaped adherend with an adhesive layer can be configured into a roll by attaching one longitudinal end of the adherend with an adhesive layer having a longitudinal direction (for example, strip-like) to a shaft such as a resin tube and winding it around the shaft.

[0053] The roll-shaped adherend with an adhesive layer of this embodiment is configured by winding the adherend with an adhesive layer in the longitudinal direction into a roll shape. Therefore, the roll-shaped adherend with an adhesive layer of this embodiment can be supplied to a highly productive roll-to-roll line, making it possible to manufacture structures at low cost. Furthermore, the roll-shaped adherend with an adhesive layer of this embodiment can be formed into adherends with adhesive layers of various dimensions by appropriately selecting the cutting position in the longitudinal direction, making it possible to apply the adherend with an adhesive layer to structures of various dimensions, thereby providing a high degree of freedom in production.

[0054] The roll-shaped adherend with an adhesive layer of this embodiment is wound into a roll, and therefore when the adherend with an adhesive layer is wound as is, the "adhesive layer" and the "back surface of the adherend," which is one layer inside, come into contact with each other. Therefore, when the adherend with an adhesive layer is pulled out from the roll-shaped adherend with an adhesive layer for use, an interlayer member in the form of a sheet or the like, intended for at least one of release and protection, can be sandwiched between the layers of the rolled adherend with an adhesive layer to enable the adherend with an adhesive layer to be pulled out more smoothly.

[0055] However, the roll-shaped adherend with an adhesive layer of this embodiment uses the adherend with an adhesive layer of Embodiment 1, which can suppress stickiness of the adhesive layer, as described above in Embodiment 1. Therefore, the roll-shaped adherend with an adhesive layer of this embodiment can also be configured so that the interlayer member described above is not sandwiched between the layers of the wound adherend with an adhesive layer. Even when such a configuration is adopted, the adherend with an adhesive layer can be smoothly pulled out because the adhesive layer is less sticky. Furthermore, in this case, no unnecessary interlayer member is generated during the production of the structure, so a roll-shaped adherend with an adhesive layer can be obtained that is advantageous in terms of cost and achieving zero emissions.

[0056] Other configurations and effects are the same as those of the adherend with an adhesive layer of the first embodiment.

[0057] (Embodiment 3) A structure of embodiment 3 will be described. The structure of this embodiment is constructed using the adherend with an adhesive layer of embodiment 1. The adherend with an adhesive layer referred to above can include an adherend with an adhesive layer that is drawn out and cut from the roll-shaped adherend with an adhesive layer of embodiment 2. Specifically, the structure has an adherend with an adhesive layer and a counter-adherend that is an adherend on the other side of the adherend provided on the adherend with an adhesive layer, and can be configured such that the adherend provided on the adherend with an adhesive layer is adhered to the surface of the counter-adherend via the adhesive layer provided on the adherend with an adhesive layer.

[0058] The counter adherend can be made of a metal material or a resin material. The material constituting the counter adherend may be the same material as the adherend provided in the adherend with the adhesive layer, or may be a different material. Furthermore, examples of the metal material and resin material constituting the counter adherend include the metal material and resin material constituting the adherend provided in the above-mentioned adherend with the adhesive layer.

[0059] Examples of the structure include heat exchangers such as radiators, evaporators, and condensers, resin housings for sensors and electronically controlled products, and various assembly components. For example, when the structure is a heat exchanger, a plate with an adhesive layer can be used as an adherend with an adhesive layer when joining fins and plates provided on the heat exchanger body of the heat exchanger. The bonded adhesive layer is in a cured state.

[0060] The structure of this embodiment is constructed using the adherend with the adhesive layer of embodiment 1, which can suppress stickiness of the adhesive layer. Therefore, the structure of this embodiment has excellent workability when handling the adherend with the adhesive layer during its production. Furthermore, the structure of this embodiment can be bonded to a counterpart adherend by heating the adherend with the adhesive layer during its production, so the step of applying a separate adhesive when bonding the adherends can be omitted. Therefore, the structure of this embodiment has excellent productivity.

[0061] Other configurations and effects are the same as those of the adherend with an adhesive layer of the first embodiment.

[0062] (Experimental example) <Material preparation> The following materials were prepared for use in producing adherends with adhesive layers in the examples and comparative examples. -Adherent- Aluminum (Al) substrate Polybutylene terephthalate (PBT) substrate Polyphenylene sulfide (PPS) substrate

[0063] -(A) Epoxy resin- Epoxy resin a1 (Mitsubishi Chemical Corporation "YX4000K", biphenyl type, unsubstituted biphenyl epoxy ratio: <1%, melting point: 105°C, crystalline) Epoxy resin a2 (Mitsubishi Chemical Corporation "YL6121HA", biphenyl type, unsubstituted biphenyl epoxy ratio: 50%, melting point: 96°C, crystalline) Epoxy resin A3 (Nippon Steel Chemical & Material Co., Ltd. "YDC-1312", hydroquinone type, melting point: 142°C, crystalline) Epoxy resin A4 (Nippon Kayaku "NC3100", biphenyl aralkyl type, softening point: 97°C) Since epoxy resin a4 is amorphous, it is not the component (A) in the present disclosure, but for convenience of explanation it is listed in the column for component (A).

[0064] -(B) Hardener- Hardener b1 (amine-based hardener) (Mitsubishi Chemical "DICY7", solid at 25°C, melting point: 208°C) Hardener b2 (amine-based hardener) (Mitsubishi Chemical "WA", liquid at 25°C) It should be noted that since curing agent b2 is a liquid at 25° C., it is not a component (B) as defined in the present disclosure, but is listed in the component (B) column for the sake of convenience.

[0065] -(C)Amorphous thermoplastic resin- Polyethersulfone (PES) (Sumitomo Chemical Co., Ltd. "5003PS", average particle size: 100 μm or less)

[0066] -(D)Other- Curing accelerator (modified imidazole) (Shikoku Kasei "2MAOK-PW", melting point: 260°C)

[0067] <Preparation of an adherend with an adhesive layer> Example 1 Epoxy resin a1, curing agent b1, polyethersulfone, and a curing accelerator were kneaded with a roll at 50°C to 120°C so as to obtain the composition (parts by mass) shown in Table 1, and then the mixture was returned to room temperature to obtain a solid curable resin composition. In preparing the curable resin composition, polyethersulfone was dispersed in particles. The obtained solid curable resin composition was then heated to 130°C to become a liquid, and then applied to one side of an aluminum adherend heated to 130°C with a bar coater to a film thickness of 100 μm, and the mixture was returned to room temperature. This yielded an adherend with an adhesive layer of Example 1.

[0068] Example 2 An adherend with an adhesive layer of Example 2 was obtained in the same manner as in Example 1, except that the composition was changed to that shown in Table 1.

[0069] Example 3 Epoxy resin a1 and polyethersulfone were heated and stirred at 130°C to achieve the composition (parts by mass) shown in Table 1, compatibilized, and then returned to room temperature (25°C). The mixture was then pulverized to a few millimeters with a hammer. The resulting pulverized epoxy resin a1, curing agent b1, and curing accelerator were then kneaded with a roll at 50°C to 120°C to achieve the composition (parts by mass) shown in Table 1, and the mixture was then returned to room temperature to obtain a solid curable resin composition. The resulting solid curable resin composition was then heated to 130°C to become liquid, and then applied to one side of an aluminum adherend heated to 130°C with a bar coater to a film thickness of 100 μm. The mixture was then returned to room temperature. This yielded an adherend with an adhesive layer of Example 3.

[0070] Example 4 An adherend with an adhesive layer of Example 4 was obtained in the same manner as in Example 1, except that the composition was changed to that shown in Table 1.

[0071] Example 5 An adherend with an adhesive layer of Example 5 was obtained in the same manner as in Example 4, except that a polybutylene terephthalate adherend was used.

[0072] Example 6 An adherend with an adhesive layer of Example 6 was obtained in the same manner as in Example 4, except that a polyphenylene sulfide adherend was used.

[0073] -Examples 7 to 15- Except for changing the compositions to be those shown in Tables 2 and 3, adherends with adhesive layers of Examples 7 to 15 were obtained in the same manner as in Example 1. However, in the preparation of adherends with adhesive layers of Examples 9, 14, and 15, the heating temperature was changed to 150°C.

[0074] -Comparative Examples 1 to 3- Except for the point that the composition was changed to be as shown in Table 4, the production was the same as in Example 1 to obtain adherends with adhesive layers of Comparative Examples 1 to 3.

[0075] <Evaluation> -Storage stability- The solid curable resin compositions prepared as described above were heated to 130°C to form a liquid, and the initial viscosity was measured. Each curable resin composition was then stored at 40°C in the atmosphere for 3 months. Each curable resin composition after storage was then heated to 130°C to form a liquid, and the viscosity after storage was measured. When the viscosity after storage was less than 2.5 times the initial viscosity, the uncured curable resin composition was deemed to have good storage stability and rated as "A." When the viscosity after storage was 2.5 times or more the initial viscosity, the uncured curable resin composition was deemed to have poor storage stability and rated as "C." The viscosity was measured using a rheometer except for Examples 8 and 9, and a thermal flow evaluation device (flow tester) for Examples 8 and 9.

[0076] -Solidification- The solid curable resin composition prepared as described above was heated to 130-150°C to liquefy it, and then applied to one side of an aluminum substrate heated to 130-150°C with a bar coater to a thickness of 100 μm. The substrate was then cooled to room temperature. After the temperature was returned to room temperature, the adhesive layer was checked for stickiness by touching it with a spatula every 10 minutes. If there was no adhesion or resistance when touching the adhesive layer within 1 hour after returning to room temperature, the adhesive layer was evaluated as having a fast solidification rate and rated as "A." If there was no adhesion or resistance when touching the adhesive layer more than 1 hour after returning to room temperature, the adhesive layer was evaluated as having a slow solidification rate and rated as "B." Note that when a spatula was lightly applied to the surface of the adhesive layer, if no adhesive was attached to the spatula, the adhesive layer was judged to have no resistance when touched. If adhesive was attached to the spatula, the adhesive layer was judged to have resistance when touched.

[0077] -Residual tackiness- An adherend of the same type and shape as the one used for the adhesive-coated adherend (adherend: 80 mm length x 20 mm width x 3 mm thickness) was placed on the adhesive layer surface of the adherend with the adhesive layer, and the two were attached together by fastening the outer edges with two clips. Kokuyo "J34D 25 mm wide" clips were used. This laminate was then left at 60-80°C for 1 hour, after which the clips were removed, and the other adherend was dropped under its own weight. If there was no visible adhesive residue on the overlapping adherend after leaving it at 80°C for 1 hour, the adhesive layer was deemed to be tack-free and stickiness was well suppressed, and a grade of "A" was given. If there was adhesive residue at 80°C, but after leaving it at 60°C for 1 hour, there was no visible adhesive residue on the overlapping adherend, and a grade of "B" was given. When adhesive residue was found, the adhesive layer before hardening was tacky and stickiness was not suppressed, so the result was rated as "C."

[0078] -Adhesive strength- To measure the adhesive strength of an adherend with an adhesive layer using an aluminum adherend, an adhesive test piece was obtained as follows. Specifically, a solid curable resin composition was applied to one side of an aluminum adherend (20 mm wide x 70 mm long x 3 mm thick) heated to 130°C, to a thickness of approximately 0.5 mm to 1 mm. Next, after confirming that the curable resin composition had become liquid, the curable resin composition was placed on top of a mating aluminum adherend (20 mm wide x 70 mm long x 3 mm thick) heated to 130°C (overlap length: 6 mm), and the two were clamped with clips. Any excess curable resin composition was removed with a spatula, and the adhesive layer was thermally cured at a curing temperature of 170°C for 2 hours. This yielded an adhesive test piece.

[0079] Furthermore, when measuring the adhesive strength of adherends with adhesive layers using polybutylene terephthalate and polyphenylene sulfide adherends, adhesive test pieces were obtained as follows. Specifically, as the polybutylene terephthalate and polyphenylene sulfide adherends, test pieces having a JIS K7139 Type A1 shape were cut in the center and the wide surfaces at both ends of the original shape were bonded together with an adhesive layer cured under the same curing conditions as above. This gave adhesive test pieces.

[0080] Using each of these adhesive test pieces, the adhesive strength was measured at room temperature at a tensile speed of 5 mm / min. The adhesive strength measured was tensile shear adhesive strength.

[0081] Details of the curable resin composition for each adherend with an adhesive layer, evaluation results, etc. are summarized in Tables 1 to 4. In each table, polyethersulfone remaining as particles (dispersed) before application to the adherend is indicated as "dispersed," and polyethersulfone that is compatible with the epoxy resin before application is indicated as "compatible."

[0082] [Table 1]

[0083] [Table 2]

[0084] [Table 3]

[0085] [Table 4]

[0086] The following can be seen from each table: In Comparative Example 1, the curable resin composition does not contain a curing agent that is solid at 25°C as the curing agent of component (B), but instead contains a curing agent that is liquid at 25°C. Therefore, in Comparative Example 1, the storage stability of the curable resin composition before curing was poor, and the adhesive layer was tacky, making it impossible to suppress sticking due to stickiness.

[0087] In Comparative Example 2, the curable resin composition does not contain a crystalline epoxy resin having a melting point of 90°C or higher as the crystalline epoxy resin of component (A), but instead contains a non-crystalline epoxy resin having a softening point of 97°C. Therefore, in Comparative Example 2, the adhesive layer was tacky, and stickiness due to stickiness could not be suppressed.

[0088] In Comparative Example 3, the curable resin composition does not contain a crystalline epoxy resin having a melting point of 90°C or higher as the crystalline epoxy resin of component (A), but instead contains a non-crystalline epoxy resin having a softening point of 97°C. Therefore, in Comparative Example 3, the adhesive layer was tacky, and stickiness due to stickiness could not be suppressed.

[0089] In contrast, Examples 1 to 15 satisfy the requirements defined in the present disclosure. Therefore, in Examples 1 to 15, the storage stability of the uncured curable resin composition was good, and stickiness of the adhesive layer could be suppressed. Furthermore, by satisfying the requirements defined in the present disclosure, Examples 1 to 15 had a solid adhesive layer before curing at room temperature, and the adhesive layer surface was not sticky, which provided excellent workability during handling. Even when heated to 80°C, the adhesive layer surface remained non-sticky. Furthermore, the adhesive layer melted, crosslinked, and cured at temperatures of 120°C to 150°C, ensuring sufficient adhesive strength between the adhesive layer and the opposing adherend.

[0090] Furthermore, when Example 1 and Example 13 are compared, it was confirmed that a higher adhesive strength can be ensured by including the amorphous thermoplastic resin of component (C) in the curable resin composition.

[0091] The present invention is not limited to the above-described embodiment and experimental examples, and various modifications are possible without departing from the spirit and scope of the present invention. Furthermore, the configurations shown in the above-described embodiment and experimental examples can be combined in any manner.

[0092] The features of the present invention are as follows. Section 1. an adherend made of a metal material or a resin material; an adhesive layer laminated on the surface of the adherend and formed from an uncured curable resin composition in a solid state at room temperature; The curable resin composition comprises (A) a crystalline epoxy resin having a melting point of 90°C or higher; (B) a curing agent that is solid at 25°C; Adherend with adhesive layer. Section 2. The curable resin composition further contains (C) an amorphous thermoplastic resin. Item 1. An adherend with an adhesive layer according to item 1. Section 3. The amorphous thermoplastic resin is polyethersulfone. Item 3. The adherend with an adhesive layer according to Item 2. Section 4. The mass ratio of the amorphous thermoplastic resin to the crystalline epoxy resin is 5% or more and 100% or less. Item 2 or Item 3. An adherend with an adhesive layer according to Item 2 or Item 3. Section 5. The amorphous thermoplastic resin exists as particles. Item 5. The adherend with an adhesive layer according to any one of items 2 to 4. Section 6. The average particle size of the particles is 0.1 μm or more and 200 μm or less. Item 6. An adherend with an adhesive layer according to item 5. Section 7. The curing agent is an amine-based curing agent having a melting point of 170°C or higher. Item 7. The adherend with an adhesive layer according to any one of items 1 to 6. Section 8. The crystalline epoxy resin has a mass ratio of an epoxy resin having a biphenyl skeleton without a substituent group of 2% or more and 60% or less. Item 8. The adherend with an adhesive layer according to any one of items 1 to 7. Section 9. Item 9. A roll-shaped adherend with an adhesive layer, in which the adherend with an adhesive layer according to any one of items 1 to 8 is wound in the longitudinal direction to form a roll. Section 10. an interlayer member having the purpose of at least one of peeling and protection is not sandwiched between the layers of the wound adherend with the adhesive layer; Item 10. A roll-shaped adherend with an adhesive layer according to Item 9. Section 11. Item 9. A structure constructed using the adherend with the adhesive layer according to any one of items 1 to 8.

Claims

1. an adherend made of a metal material or a resin material; an adhesive layer laminated on the surface of the adherend and formed from an uncured curable resin composition in a solid state at room temperature; The curable resin composition comprises (A) a crystalline epoxy resin having a melting point of 90°C or higher; (B) a curing agent that is solid at 25°C; Adherend with adhesive layer.

2. The curable resin composition further contains (C) an amorphous thermoplastic resin, The adherend with the adhesive layer according to claim 1 .

3. The curing agent is an amine-based curing agent having a melting point of 170°C or higher. The adherend with the adhesive layer according to claim 1 .

4. The amorphous thermoplastic resin is polyethersulfone. The adherend with the adhesive layer according to claim 2 .

5. a mass ratio of the amorphous thermoplastic resin to the crystalline epoxy resin is 5% or more and 100% or less; The adherend with the adhesive layer according to claim 2 .

6. The crystalline epoxy resin has a mass ratio of an epoxy resin having a biphenyl skeleton without a substituent group of 2% or more and 60% or less. The adherend with the adhesive layer according to claim 1 .

7. The amorphous thermoplastic resin exists as particles. The adherend with the adhesive layer according to claim 2 .

8. The average particle size of the particles is 0.1 μm or more and 200 μm or less. The adherend with the adhesive layer according to claim 7.

9. A roll-shaped adherend with an adhesive layer, wherein the adherend with an adhesive layer according to any one of claims 1 to 8 is wound in the longitudinal direction to form a roll.

10. an interlayer member having the purpose of at least one of peeling and protection is not sandwiched between the layers of the wound adherend with the adhesive layer; The roll-shaped adherend with an adhesive layer according to claim 9.

11. A structure constructed using the adherend with the adhesive layer according to any one of claims 1 to 8.

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