TW202233780A - adhesive sheet - Google Patents

Abstract

Provided is an adhesive sheet that has excellent adherend visibility (visibility through the adhesive sheet) and that has excellent adhesiveness and detachability. The adhesive sheet according to the present invention is provided with a gas generation layer that generates a gas when being irradiated with laser light, and has a haze value of 50% or less. In one embodiment, the thickness of the gas generation layer is 0.1-50 [mu]m. In one embodiment, the gas generation layer is a layer capable of absorbing ultraviolet rays. In one embodiment, the gas generation layer contains an ultraviolet absorber.

Description

adhesive sheet

The present invention relates to an adhesive sheet.

In the past, when processing (processing) electronic parts, there were cases where the object to be processed was temporarily fixed to a fixing table through an adhesive sheet during processing, and the object to be processed was removed from the adhesion after processing. Sheet peeling. As the adhesive sheet used in such an operation, there is a case where an adhesive sheet is used which has a specific adhesive force at the time of processing, and the adhesive force can be lowered after the treatment. As one of such adhesive sheets, an adhesive sheet composed of thermally expandable microspheres contained in an adhesive layer has been proposed (for example, Patent Document 1). The adhesive sheet containing heat-expandable microspheres has the following characteristics: it has a specific adhesive force, and by heating the heat-expandable microspheres to expand, irregularities are formed on the adhesive surface, so that the contact area is reduced, and the adhesive force is reduced. or disappear. Such an adhesive sheet has the advantage that the object to be treated can be easily peeled off without external stress.

However, the light transmittance of the adhesive sheet containing the thermally expandable microspheres is low, and when the adhesive sheet is used, the following problem arises: it is difficult to view the temporary fixed position of the display electronic parts through the adhesive sheet and install it on the The marking of the fixed table. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2001-131507

[Problems to be Solved by Invention]

The present invention has been accomplished in order to solve the aforementioned problems, and an object of the present invention is to provide an adhesive sheet which achieves both excellent adhesiveness and releasability, and which is excellent in the visibility of the attached body (visibility through the adhesive sheet). [Technical means to solve problems]

The adhesive sheet of the present invention includes a gas generating layer that generates gas by irradiation with laser light, and has a haze value of 50% or less. In one embodiment, the thickness of the gas generating layer is 0.1 μm˜50 μm. In one embodiment, the gas generating layer is a layer that can absorb ultraviolet rays. In one embodiment, the gas generating layer contains an ultraviolet absorber. In one embodiment, the ultraviolet transmittance at a wavelength of 360 nm of the adhesive sheet is 30% or less. In one embodiment, the ultraviolet transmittance of the above-mentioned adhesive sheet with a wavelength of 500 nm is 50% to 100%. In one embodiment, the gas generating layer is a layer that generates hydrocarbon-based gas. In one embodiment, the gasification initiation temperature of the gas generating layer is 150°C to 500°C. In one embodiment, the 10% weight reduction temperature of the adhesive sheet is 200°C to 500°C. In one embodiment, the adhesive sheet is further provided with an adhesive layer on at least one side of the gas generating layer, and the adhesive layer is a layer whose surface is deformed by irradiating the adhesive sheet with laser light. In one embodiment, the thickness of the adhesive layer is 0.1 μm˜50 μm. In one embodiment, the adhesive layer is foamed by irradiating the adhesive sheet with laser light. According to another aspect of the present invention, a method for processing electronic parts is provided. The processing method of the electronic component includes: attaching the electronic component to the above-mentioned adhesive sheet; and irradiating the adhesive sheet with laser light to peel off the electronic component from the adhesive sheet. In one embodiment, the peeling of the above-mentioned electronic components is performed at selected positions. In one embodiment, the processing method includes: performing specific processing on the electronic component after the electronic component is attached to the adhesive sheet and before the electronic component is peeled off from the adhesive sheet. In one embodiment, the above-mentioned treatment is grinding, cutting, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer printing, alignment, repair, or device surface protection. According to another aspect of the present invention, a method for processing electronic parts is provided. The processing method of this electronic component includes arranging the electronic component on another sheet after peeling the electronic component from the adhesive sheet. [Effect of invention]

According to the present invention, it is possible to provide an adhesive sheet that achieves both excellent adhesiveness and releasability, and that is excellent in the visibility of the adhered body (visibility through the adhesive sheet).

A. Outline of Adhesive Sheet FIG. 1( a ) is a schematic cross-sectional view of an adhesive sheet according to a preferred embodiment of the present invention. The adhesive sheet 100 includes the gas generating layer 10 . The gas generating layer 10 generates gas by irradiation with laser light. More specifically, the gas generating layer 10 is a layer that generates gas by vaporizing its components by irradiation with laser light. As the laser light, UV (ultraviolet) laser light is typically used. The gas generating layer 10 may have a specific adhesive force.

Fig. 1(b) is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention. The adhesive sheet 100 ′ includes the gas generating layer 10 and the adhesive layer 20 arranged on at least one layer on one side of the gas generating layer 10 . The surface of the adhesive layer 20 is deformed by irradiating the adhesive sheet (substantially the gas generating layer) with laser light. In one embodiment, the deformation occurs on the opposite side of the adhesive layer 20 from the gas generating layer 10 due to the gas generated from the gas generating layer 10 .

The adhesive sheet of the present invention can be used by adhering a to-be-processed object such as an electronic component to a gas generating layer or an adhesive layer. The pressure-sensitive adhesive sheet of the present invention is provided with a gas generating layer, and generates gas locally in a small area by laser light irradiation. By the generation of such a gas, deformation of the attached surface occurs, and as a result, the adherend can be peeled off favorably. When the adhesive sheet has an adhesive layer, as described above, the adhesive layer is deformed due to the generation of the gas, and as a result, the part irradiated with laser light exhibits peelability. Typically, the laser light is irradiated from the opposite side of the gas generating layer from the adhesive layer. According to the present invention, deformation can be generated in a minute range as described above, so that when handling (processing) an extremely fine small electronic component, the small electronic component can be peeled off favorably. In addition, even when the small electronic components that need to be peeled off and the small electronic components that do not need to be peeled off are temporarily fixed adjacent to each other, the peeling can be performed at the site of the peeling object, and the peeling can be performed at the site other than the peeling object. Only the small electronic parts that need to be peeled off can be peeled off, and the unwanted detachment of the small electronic parts can also be prevented. In order to generate the deformation of the adhesive layer well, it is preferable to block in such a way that at least a part of the generated gas does not escape from the adhesive sheet, and the adhesive layer can function as a gas barrier layer.

之UV雷射光，於0.80 mW功率、40 kHz頻率下進行脈衝掃描，而自氣體產生層產生氣體。關於變形後之形狀，例如對於脈衝掃描過之任意1點，於雷射光照射結束24小時後，根據共聚聚焦雷射顯微鏡或非接觸型干涉顯微鏡(WYKO)等之測定進行觀測。其形狀可為發泡(凸)、貫通孔(凹凸)、凹陷(凹)，藉由該等變形而可產生剝離性。於要沿法線方向將電子零件效率良好地剝離時，較佳為雷射光照射前後之法線方向之位移變化較大，尤其適合形成發泡形狀者。發泡(凸)係以未照射部之黏著片材表面為基準，將最高點定義為垂直位移Y，將半峰全幅值定義為水平位移X(直徑)。關於雷射光照射後形成孔之貫通孔(凹凸)與凹陷(凹)，將最高點與最低點之差定義為垂直位移Y，將孔之直徑定義為水平位移X。以下，亦將藉由雷射光照射而變形之部分稱為｢變形部｣。 The so-called deformation of the adhesive layer refers to the displacement generated in the normal direction (thickness direction) and the horizontal direction (direction orthogonal to the thickness direction) of the adhesive layer. Deformation of the adhesive layer is produced, for example, by using a wavelength of 355 nm and a beam diameter of about 20 μm

The UV laser light is pulsed at 0.80 mW power and 40 kHz frequency, and gas is generated from the gas generating layer. The shape after deformation is observed, for example, by measurement of a confocal laser microscope or a non-contact interference microscope (WYKO) 24 hours after the completion of laser light irradiation at any point scanned by the pulse. Its shape can be foamed (convex), through-hole (concave-convex), and concave (concave), and releasability can be produced by these deformations. When the electronic parts are to be efficiently peeled off along the normal direction, it is preferable that the displacement in the normal direction before and after the laser light irradiation changes greatly, and it is especially suitable for forming a foamed shape. Foaming (convex) is based on the surface of the adhesive sheet in the unirradiated part, the highest point is defined as vertical displacement Y, and the full width at half maximum is defined as horizontal displacement X (diameter). Regarding the through-hole (concave-convex) and concave (concave) formed holes after laser irradiation, the difference between the highest point and the lowest point is defined as the vertical displacement Y, and the diameter of the hole is defined as the horizontal displacement X. Hereinafter, the portion deformed by the irradiation of laser light is also referred to as a "deformed portion".

2 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention. The adhesive sheet 200 further includes an intermediate layer 30 between the gas generating layer 10 and the adhesive layer 20 . By providing the intermediate layer, the deformation of the adhesive layer can be easily controlled (details will be described later). In addition, the intermediate layer may function as a gas barrier layer in cooperation with the adhesive layer. Therefore, by providing the intermediate layer, the gas barrier properties are improved, and an adhesive sheet with a better deformation of the adhesive layer can be obtained. The intermediate layer may be a single layer or a plurality of layers.

Although not shown, the above-mentioned adhesive sheet may further include other layers. For example, a base material, another adhesive layer, etc. may be provided on the surface of the gas generating layer on the opposite side to the adhesive layer. As the base material, for example, a film containing any appropriate resin is used.

The adhesive sheet of the present invention is characterized in that the haze value is 50% or less. In the present invention, the gas generating layer, the adhesive layer, and the intermediate layer can be formed without insoluble fillers, so that an adhesive sheet with low haze value, high light transmittance, and suppressed white turbidity can be obtained. The above-mentioned adhesive sheet has high transparency before laser irradiation (at the time of temporary fixation). If such an adhesive sheet is used, for example, an adherend (for example, a table for temporarily fixing electronic components) can be visually recognized through the adhesive sheet, and, for example, a display electronic component can be preferably viewed through the adhesive sheet. The temporary fixed position is set on the mark on the fixed table. Such an effect is an excellent effect that cannot be obtained by an adhesive sheet containing an insoluble filler (for example, an adhesive sheet containing thermally expandable microspheres in an adhesive layer serving as a releasable presentation layer).

The haze value of the adhesive sheet of the present invention is preferably 0% to 50%, more preferably 0.01% to 40%, further preferably 0.05% to 30%, particularly preferably 0.1% to 20%. Within such a range, the above-mentioned effects of the present invention become more remarkable.

The adhesive force of the adhesive layer of the adhesive sheet of the present invention to SUS430 is preferably 0.1 N/20 mm or more, more preferably 0.2 N/20 mm to 50 N/20 mm, and more preferably 0.5 N/20 mm ~40 N/20 mm, preferably 0.7 N/20 mm ~ 20 N/20 mm, and most preferably 1 N/20 mm ~ 10 N/20 mm. Within such a range, for example, an adhesive sheet which exhibits good adhesiveness can be obtained as a temporary fixing sheet used in the manufacture of electronic parts. In this specification, the so-called adhesive force refers to the method in accordance with JIS (Japanese Industrial Standards) Z 0237: 2000 under the environment of 23°C (bonding conditions: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180°) and the measured adhesive force.

In one embodiment, the gas generating layer has a specific adhesive force. The adhesive force of the gas generating layer of the adhesive sheet of the present invention to SUS430 is preferably 0.1 N/20 mm or more, more preferably 0.5 N/20 mm to 50 N/20 mm, and more preferably 1 N/20 mm ~40 N/20 mm, preferably 1.5 N/20 mm ~ 30 N/20 mm, and most preferably 2 N/20 mm ~ 20 N/20 mm. Within such a range, for example, an adhesive sheet which exhibits good adhesiveness can be obtained as a temporary fixing sheet used in the manufacture of electronic parts.

The thickness of the adhesive sheet of the present invention is preferably 2 μm to 200 μm, more preferably 3 μm to 150 μm, and still more preferably 5 μm to 120 μm.

The water vapor transmission rate of the adhesive sheet of the present invention is preferably 5000 g/(m ² ·day) or less, more preferably 4800 g/(m ² ·day) or less, still more preferably 4500 g/(m ² ·day) or less day) or less, more preferably 4200 g/(m ² ·day) or less. In an adhesive sheet with an adhesive layer (and an intermediate layer if necessary) having a water vapor transmission rate of this range, the escape of gas generated by irradiation with laser light is prevented, and the adhesive layer is formed into an excellent shape. Deformation Department. When such an adhesive sheet is used, a small to-be-adhered body (for example, an electronic component) can be peeled off with high precision. The water vapor transmission rate of the adhesive sheet of the present invention is preferably as small as possible, and the lower limit thereof is, for example, 0.1 g/(m ² ·day). The water vapor transmission rate can be measured by the measurement method according to JIS K7129B in an environment of 30°C and 90% RH.

The water vapor transmission rate of the laminate comprising the above-mentioned adhesive layer and the intermediate layer is preferably 10000 g/(m ² ·day) or less, more preferably 7000 g/(m ² ·day) or less, and still more preferably 5000 g /(m ² ·day) or less, more preferably 4800 g/(m ² ·day) or less, more preferably 4500 g/(m ² ·day) or less, most preferably 4200 g/(m ² ·day) the following. Within such a range, the laminate including the adhesive layer and the intermediate layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed in the adhesive layer. When such an adhesive sheet is used, a small to-be-adhered body (for example, an electronic component) can be peeled off with high precision. The water vapor transmission rate of the laminate including the adhesive layer and the intermediate layer is preferably as small as possible, and the lower limit is, for example, 1 g/(m ² ·day).

The puncture strength of the laminate comprising the above-mentioned adhesive layer and the intermediate layer is preferably 10 mN to 5000 mN, more preferably 30 mN to 4000 mN, further preferably 50 mN to 3000 mN, particularly preferably 100 mN to 2000 mN mN. Within such a range, the laminate including the adhesive layer and the intermediate layer functions well as a gas barrier layer, and the shape change due to the generation of gas preferably occurs, and as a result, the adhesive layer is formed Deformation part of excellent shape. When such an adhesive sheet is used, a small to-be-adhered body (for example, an electronic component) can be peeled off with high precision. The puncture strength is shown in Fig. 3. Using a compression tester 6 (manufactured by Kato Tech, trade name "KES-G5"), a sample 4 (for example, a laminate) is sandwiched between a circular opening having a diameter of 11.28 mm. The sample holders 5A and 5B are used for measurement. More specifically, at a measurement temperature of 23°C, a puncture needle (curvature radius: 1 mm) can be punctured into the sample at the center of the circular opening of the circular opening (puncturing speed: 0.1 mm/s), The maximum load at the rupture point was taken as the puncture strength.

The ultraviolet transmittance at a wavelength of 360 nm of the laminate comprising the above-mentioned adhesive layer and the intermediate layer is preferably 50% to 100%, more preferably 60% to 95%.

The ultraviolet transmittance of the above-mentioned adhesive sheet at a wavelength of 360 nm is preferably 30% or less, more preferably 20% or less, further preferably 15% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the ultraviolet transmittance at the wavelength of 360 nm of the adhesive sheet is, for example, 0% (preferably 0.05%, more preferably 0.1%).

The ultraviolet transmittance of the above-mentioned adhesive sheet having a wavelength of 500 nm is preferably 50% to 100%, more preferably 60% to 99%, further preferably 70% to 98%, particularly preferably 80% to 97%.

The 10% weight reduction temperature of the above-mentioned adhesive sheet is preferably 200°C to 500°C, more preferably 220°C to 450°C, further preferably 250°C to 400°C, particularly preferably 270°C to 370°C. Within such a range, an adhesive sheet that can form a better deformed portion by laser light irradiation can be obtained. The 10% weight reduction temperature of the adhesive sheet means that in the TGA analysis when the adhesive sheet is heated up, the weight of the adhesive sheet is reduced by 10% by weight relative to the weight before heating (that is, the weight of the adhesive sheet becomes 90% relative to the weight before irradiation). %) the temperature at the time point.

B. Gas-generating layer The gas-generating layer can be a layer that can absorb ultraviolet rays. In one embodiment, the gas generating layer contains an ultraviolet absorber. By containing an ultraviolet absorber, a gas generating layer that can absorb and vaporize the laser light can be formed. Typically, the gas generating layer contains an ultraviolet absorber and an adhesive A. Preferably, the ultraviolet absorber is dissolved in the adhesive A and exists. If the ultraviolet absorber is dissolved in the adhesive A, an adhesive sheet can be obtained that can generate deformed parts (for example, uneven parts) on any part of the adhesion surface (the surface of the gas generating layer and/or the surface of the adhesive layer). ), and the deviation of the shape of the deformed part (eg, the concave-convex part) is small. When such an adhesive sheet is used, a deformation|transformation part (for example, uneven|corrugated part) can be precisely produced|generated in a desired part, and the effect of this invention becomes remarkable. In addition, in this specification, the state "dissolved in the adhesive and exists" means that the ultraviolet absorber does not exist in the gas generating layer in the form of particles. More specifically, the gas generating layer preferably does not contain an ultraviolet absorber having a particle size of 10 μm or more in particle distribution measurement in the cross section of the gas generating layer by X-ray CT (computer tomography). Furthermore, the gas generating layer may or may not contain an insoluble component in the adhesive. In one embodiment, the presence or absence and content of the insoluble components in the gas generating layer are evaluated by the haze value of the gas generating layer, and the smaller the haze value is, the less the content of the insoluble components in the gas generating layer is evaluated. It is preferable that the gas generating layer contains substantially no insoluble components in the adhesive.

The elastic modulus of the cross section of the gas generating layer obtained by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. Within such a range, the shape change of the gas generating layer due to the generation of the gas preferably occurs, and as a result, the adhering surface (the surface of the gas generating layer and/or the surface of the adhesive layer) is formed with an excellent shape. Deformation Department. The so-called elastic modulus obtained by the nanoindentation method refers to the continuous measurement of the load load and the indentation depth of the indenter when the indenter is pressed into the sample (for example, the adhesive surface) when it is spanned and loaded, and when it is unloaded. And according to the obtained load load-indentation depth curve to calculate the elastic modulus. The elastic modulus obtained by the nanoindentation method is obtained as follows: For the displacement obtained by pressing a diamond-made Berkovich type (triangular pyramid type) probe vertically against the section cut out of the measurement object layer - The load hysteresis curve was numerically processed using the software (triboscan) attached to the measuring device. In this specification, the elastic modulus of the cross section obtained by the nanoindentation method is obtained by using a nanoindenter (Triboindenter TI-950 manufactured by Hysitron Inc.) by a single indentation at a specific temperature (25°C). The elastic modulus was measured under the measurement conditions of the indentation speed of about 500 nm/sec, the extraction speed of about 500 nm/sec, and the indentation depth of about 1500 nm. Furthermore, the elastic modulus of the gas generating layer can be adjusted by the kind of material contained in the layer, the structure of the base polymer constituting the material, the kind and amount of additives added to the layer, and the like. Furthermore, in this specification, when the cross-section or surface is not mentioned and only the elastic modulus obtained by the nano-indentation method is described, the elastic modulus refers to the elastic modulus of the cross-section obtained by the nano-indentation method.

The elastic modulus of the surface of the gas generating layer obtained by the nano-indentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. Within such a range, a change in the shape of the gas generating layer due to gas generation is preferably generated, and as a result, a deformed portion having an excellent shape is formed in the adhesive layer. The so-called elastic modulus obtained by the nanoindentation method refers to the continuous measurement of the load load and the indentation depth of the indenter when the indenter is pressed into the sample (for example, the adhesive surface) when it is spanned and loaded, and when it is unloaded. And according to the obtained load load-indentation depth curve to calculate the elastic modulus. The elastic modulus obtained by the nanoindentation method is obtained as follows: For the displacement obtained by pressing a diamond-made Berkovich type (triangular pyramid type) probe vertically against the section cut out of the measurement object layer - The load hysteresis curve was numerically processed using the software (triboscan) attached to the measuring device. In this specification, the so-called elastic modulus of the surface obtained by the nanoindentation method is a nanoindenter (Triboindenter TI-950 manufactured by Hysitron Inc.), by a single indentation at a specific temperature (25°C). The elastic modulus was measured under the measurement conditions of the indentation speed of about 500 nm/sec, the extraction speed of about 500 nm/sec, and the indentation depth of about 3000 nm. Furthermore, the elastic modulus of the gas generating layer can be adjusted by the kind of material contained in the layer, the structure of the base polymer constituting the material, the kind and amount of additives added to the layer, and the like. In the present invention, the elastic modulus obtained by the nanoindentation method measured by the above method with the cross section as the measurement surface, and the elasticity obtained by the nanoindentation method measured by the above method with the surface as the measurement surface There is no significant difference in modulus, and the value measured from the surface can be used as the measured value from the cross-section when it is difficult to measure from the cross-section.

The gasification initiation temperature of the gas generating layer is preferably 150°C to 500°C, more preferably 170°C to 450°C, further preferably 190°C to 420°C, particularly preferably 200°C to 400°C. Within such a range, an adhesive sheet that can form a better deformed portion by laser light irradiation can be obtained. In addition, in this specification, the vaporization initiation temperature of the gas generating layer means the gas generating rising temperature calculated from EGA analysis (evolved gas analysis, evolved gas analysis) when raising the temperature of the adhesive sheet. The so-called rising temperature of gas generation is defined as the temperature which reaches the half value of the maximum gas generation peak of the EGA/MS spectrum obtained by EGA analysis. The lower the starting temperature of vaporization, the lower the temperature at which the gas starts to be generated when the laser light is irradiated, and a sufficient amount of gas will be generated when the laser light is irradiated with a smaller power. In one embodiment, the vaporization initiation temperature of the gas generating layer corresponds to the vaporization initiation temperature of the ultraviolet absorber.

The 10% weight reduction temperature of the gas generating layer is preferably 150°C to 500°C, more preferably 170°C to 450°C, and still more preferably 200°C to 400°C. Within such a range, an adhesive sheet that can form a better deformed portion by laser light irradiation can be obtained. The so-called 10% weight reduction temperature of the gas-generating layer refers to the weight of the gas-generating layer relative to the temperature in TGA analysis (thermogravimetric analysis, thermogravimetric analysis) when the adhesive sheet is heated up (for example, when the temperature is raised by laser light irradiation). The temperature at the time point at which the weight of the gas generating layer is reduced by 10% by weight from the previous weight (that is, the weight of the gas generating layer becomes 90% with respect to the weight before the temperature increase).

The thickness of the gas generating layer is preferably 0.1 μm to 50 μm, more preferably 1 μm to 40 μm, further preferably 2 μm to 30 μm, particularly preferably 5 μm to 20 μm. Within such a range, an adhesive sheet that can form a better deformed portion by laser light irradiation can be obtained.

The elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] of the gas generating layer obtained by the nanoindentation method satisfy the following formula (1). Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^-0.116・・・(1) In the present invention, by configuring the gas generating layer so as to satisfy the above-mentioned formula (1), it is possible to prevent the Excessive deformation caused by the gas generated by the layer is generated, so that the adhesive sheet is well deformed by the irradiation of the laser light. By forming such a gas generating layer, surface deformation in a small range can be generated without disposing a thicker barrier layer (adhesive layer) as a layer for preventing excessive deformation. More specifically, the surface can be deformed by the gas generating layer alone, or an adhesive layer (gas barrier layer) can be formed flexibly.

In one embodiment, the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] obtained by the nanoindentation method satisfy the following formula (2). In one embodiment, the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] obtained by the nanoindentation method satisfy the following formula (3). Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^-0.092・・・(2) Log(Er(gas)×10 ⁶ )≧7.52×h(gas) ^-0.081・・・(3) Within such a range, the above-mentioned effect becomes more remarkable.

In one embodiment, the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] obtained by the nanoindentation method further satisfy the following formula (4). Log(Er(gas)×10 ⁶ )≦47.675×h(gas) ^-0.519・・・(4)

The ultraviolet transmittance of the above-mentioned gas generating layer having a wavelength of 360 nm is preferably 30% or less, more preferably 20% or less, further preferably 15% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the ultraviolet transmittance of the wavelength 360 nm of the gas generating layer is, for example, 0% (preferably 0.05%, more preferably 0.1%).

The haze value of the gas generating layer is preferably 55% or less, more preferably 0.1% to 50%, and still more preferably 0.5% to 40%. The haze value becomes an indicator of the compatibility of the adhesive (substantially the base polymer) and the ultraviolet absorber in the gas generating layer. The haze value is obtained from the ratio of diffuse transmitted light to total light transmitted light when light in the visible light region (wavelength: 380 nm to 780 nm) is incident. Considering the wavelength size of light as the smallest unit, when the concentration and composition are uniform above the wavelength size, the transparency is high, that is, the compatibility is high. On the other hand, when the concentration and the composition are not uniform, scattering of light occurs and cloudiness occurs, that is, compatibility becomes low. When the haze of the gas generating layer is in the above-mentioned range, an adhesive sheet in which the ultraviolet absorber exists without bias can be obtained. Such an adhesive sheet precisely expresses peelability by laser light irradiation.

B-1. UV Absorber As the ultraviolet absorber, any appropriate ultraviolet absorber can be used as long as the effect of the present invention is obtained. As the ultraviolet absorber, for example, a benzophenone-based ultraviolet absorber, a trisulfan-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylate-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber may, for example, be mentioned. absorbent, etc. Among them, three-series ultraviolet absorbers are preferred. Especially in the case of using an acrylic adhesive as the adhesive A, the tri-type ultraviolet absorber can be preferably used because of its high compatibility with the base polymer of the acrylic adhesive. By using a three-series ultraviolet absorber, a gas generating layer with a small haze value can be formed. The tris'-based ultraviolet absorber is more preferably a compound having a hydroxyl group, and particularly preferably an ultraviolet absorber comprising a hydroxyphenyl tris'-based compound (hydroxyphenyl tris-based ultraviolet absorber).

As a hydroxyphenyl tris-based ultraviolet absorber, for example, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl)- Reaction product of 5-hydroxybenzene and [(C10-C16 (mainly C12-C13)alkoxy)methyl]oxirane (trade name "TINUVIN 400", manufactured by BASF Corporation), 2-[4,6 -Bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-Dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-tris(2-ethylhexyl)-glycidic acid Reaction product of ester (trade name "TINUVIN 405", manufactured by BASF Corporation), 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl) -1,3,5-Tris(trade name "TINUVIN 460", manufactured by BASF Corporation), 2-(4,6-diphenyl-1,3,5-tris-2-yl)-5-[ (hexyl)oxy]phenol (trade name "TINUVIN 1577", manufactured by BASF Corporation), 2-(4,6-diphenyl-1,3,5-tris-2-yl)-5-[2- (2-ethylhexyloxy)ethoxy]phenol (trade name "Adekastab LA-46", manufactured by ADEKA Co., Ltd.), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy] base]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-tris(trade name "TINUVIN 479", manufactured by BASF Corporation), trade name "TINUVIN 477 manufactured by BASF Corporation" "Wait.

Examples of benzotriazole-based ultraviolet absorbers (benzotriazole-based compounds) include 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (trade name "" TINUVIN PS", manufactured by BASF Corporation), phenylpropionic acid, and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and straight-chain alkyl) ester compound (trade name "TINUVIN 384-2", manufactured by BASF Corporation), 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzo octyl triazol-2-yl)phenyl]propionate and 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate Mixture of acid 2-ethylhexyl ester (trade name "TINUVIN 109", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1- Phenylethyl)phenol (trade name "TINUVIN 900", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)- 4-(1,1,3,3-Tetramethylbutyl)phenol (trade name "TINUVIN 928", manufactured by BASF), 3-(3-(2H-benzotriazol-2-yl)-5- The reaction product of methyl tert-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 (trade name "TINUVIN 1130", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl) ) p-cresol (trade name "TINUVIN P", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol (trade name "TINUVIN 234", manufactured by BASF Corporation), 2-[5-chloro-2H-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (trade name "TINUVIN 326", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (trade name "TINUVIN 328", manufactured by BASF Corporation), 2 -(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (trade name "TINUVIN 329", manufactured by BASF Corporation), 2,2'- Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (trade name "TINUVIN 360", manufactured by BASF Corporation ), the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 (trade name " TINUVIN 213", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (trade name "TINUVIN 571", BASF company), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole (trade name "Sumisorb 250", manufactured by Sumitomo Chemical Co., Ltd.), 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole (trade name "SEESORB" 703", manufactured by Shipro Kasei Corporation), 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimide Methyl)phenol (trade name "SEESORB 706", manufactured by Shipro Kasei Corporation), 2-(4-benzyloxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole (Shipro Kasei Corporation) Manufactured under the trade name "SEESORB 7012BA"), 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (trade name "KEMISORB 73", Chemipro Kasei Corporation), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (trade name "Adekastab LA-31", ADEKA Corporation Co., Ltd.), 2-(2H-benzotriazol-2-yl)-p-cresol (trade name "Adekastab LA-32", manufactured by ADEKA Co., Ltd.), 2-(5-chloro-2H-benzoyl) Triazol-2-yl)-6-tert-butyl-4-methylphenol (trade name "Adekastab LA-36", manufactured by ADEKA Co., Ltd.) and the like.

In one embodiment, a halogen-free UV absorber is used. When such an ultraviolet absorber is used, an adhesive sheet which is hard to contaminate an adherend such as an electrode can be obtained.

200-1500 are preferable, as for the molecular weight of the compound which comprises the said ultraviolet absorber, 250-1200 are more preferable, and 300-1000 are still more preferable. Within such a range, an adhesive sheet that can form a better deformed portion by laser light irradiation can be obtained.

The maximum absorption wavelength of the above-mentioned ultraviolet absorber is preferably 300 nm to 450 nm, more preferably 320 nm to 400 nm, and still more preferably 330 nm to 380 nm.

The content ratio of the ultraviolet absorber is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and still more preferably 5 to 30 parts by weight relative to 100 parts by weight of the gas generating layer. Within such a range, an adhesive sheet that can form a better deformed portion by laser light irradiation can be obtained.

B-2. Adhesive A As the adhesive A contained in the above-mentioned gas generating layer, the pressure-sensitive adhesive A is preferably used. Examples of the adhesive A include acrylic adhesives, rubber-based adhesives, vinyl alkyl ether-based adhesives, silicone-based adhesives, polyester-based adhesives, polyamide-based adhesives, amine-based adhesives Formate based adhesives, styrene-diene block copolymer based adhesives, etc. Among them, an acrylic adhesive or a rubber-based adhesive is preferable, and an acrylic adhesive is more preferable. In addition, the said adhesive can be used individually or in combination of 2 or more types.

As the above-mentioned acrylic adhesive, for example, an acrylic polymer (homopolymer or copolymer) using one or two or more of alkyl (meth)acrylates as a monomer component can be mentioned as a base polymer. Acrylic adhesives, etc. Specific examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, Butyl (meth)acrylate, isobutyl (meth)acrylate, 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylate Base) isononyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate Tridecyl acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate , C1-20 alkyl esters of (meth)acrylates such as octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. Among them, alkyl (meth)acrylates having linear or branched alkyl groups with 1 to 20 carbon atoms can be preferably used, and those with 2 to 20 carbon atoms can be preferably used. Alkyl (meth)acrylate of an alkyl-like or branched-like group.

In one embodiment, alkyl (meth)acrylate A having a linear or branched alkyl group having a carbon number of 4 or more (preferably 4 to 20, more preferably 4 to 18) is used. An acrylic polymer having a long side chain formed using such a monomer is advantageous in that the affinity (compatibility) with the ultraviolet absorber is high. The content ratio of the above-mentioned alkyl (meth)acrylate A is preferably 30% by weight or more, more preferably 50% by weight or more, and still more preferably 70% by weight to 100% by weight with respect to all the structural units constituting the acrylic polymer. % by weight, more preferably 80% by weight to 100% by weight. Within such a range, the compatibility between the acrylic polymer and the ultraviolet absorber can be improved. With respect to 100 parts by weight of the total amount of the acrylic polymer, the content ratio of the acrylic polymer including the structural unit derived from the above-mentioned alkyl (meth)acrylate A is preferably 30 parts by weight to 100 parts by weight, more preferably 70 to 100 parts by weight.

In one embodiment, alkyl (meth)acrylate A having a linear or branched alkyl group having a carbon number of 4 or more (preferably 4 to 20, more preferably 4 to 18) is used in combination , and three 𠯤 UV absorbers. In particular, the alkyl (meth)acrylate A has excellent compatibility with the tris-based ultraviolet absorber, and the visibility of the adhesive sheet having the gas generating layer formed using these compounds is remarkably excellent.

The said acrylic polymer can also contain the unit corresponding to the other monomer component which can be copolymerized with the said alkyl (meth)acrylate for the purpose of improvement, such as cohesion force, heat resistance, crosslinking property, etc. as needed. Examples of such monomer components include carboxyl-containing groups such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Monomers; anhydride monomers such as maleic anhydride and itaconic anhydride; (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth)acrylic acid Hydroxyhexyl, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate, etc. body; styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate , (meth)acryloyloxynaphthalenesulfonic acid and other monomers containing sulfonic acid groups; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-butyl (methyl) (N-substituted) amide monomers such as acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc.; (meth)acrylate amine Aminoalkyl (meth)acrylate monomers such as ethyl ethyl ester, N,N-dimethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, etc.; ( (meth)acrylic acid alkoxyalkyl ester monomers such as methoxyethyl meth)acrylate and ethoxyethyl (meth)acrylate; N-cyclohexylmaleimide, N- Isopropyl maleimide, N-lauryl maleimide, N-phenylmaleimide and other maleimide monomers; N-methyl Iconimide, N-Ethyl Iconimide, N-Butyl Iconimide, N-Octyl Iconimide, N-2-Ethylhexyl Iconimide, N -Iconimide monomers such as Cyclohexyl Iconimide, N-Lauryl Iconimide, etc.; Butadiimide such as meth)acryloyl-6-oxyhexamethylene butadiimide, N-(meth)acryloyl-8-oxyoctamethylene butadiimide, etc. Monomers; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidone, vinyl Ethylene such as pyridine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylpyridine, N-vinylcarboxyamide, styrene, α-methylstyrene, N-vinylcaprolactam base monomers; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; acrylic monomers containing epoxy groups such as glycidyl (meth)acrylate; (meth)acrylic acid polyethylene glycol, ( Glycol acrylate monomers such as meth)acrylic acid polypropylene glycol, (meth)acrylic acid methoxyethylene glycol, (meth)acrylic acid methoxypolypropylene glycol; (meth)acrylic acid tetrahydrofuran methyl ester, fluorine (methyl) base) acrylate, silicone (meth)acrylate and other acrylate monomers with heterocycle, halogen atom, silicon atom, etc.; hexanediol di(meth)acrylate, (poly)ethylene glycol di( Meth)acrylate, (poly)propylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate , Dipentaerythritol hexa(meth)acrylate, epoxy acrylate, acrylic polyester, acrylic urethane and other multifunctional monomers; Isoprene, butadiene, isobutylene and other olefin monomers; Vinyl ether and other vinyl ether-based monomers. These monomer components may be used alone or in combination of two or more. Among them, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and maleic acid are preferably used from the viewpoint of high affinity (compatibility) with the ultraviolet absorber. Carboxyl-containing monomers such as diacid, fumaric acid and crotonic acid; acid anhydride monomers such as maleic anhydride and itaconic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate , hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, methacrylic acid ( Hydroxyl-containing monomers such as 4-hydroxymethylcyclohexyl) methyl ester. The content ratio of the carboxyl group-containing monomer is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, and more preferably 3 parts by weight relative to 100 parts by weight of the total amount of the acrylic polymer parts to 9.5 parts by weight. The content ratio of the acid anhydride monomer is preferably 0.5 parts by weight to 15 parts by weight, more preferably 1 part by weight to 10 parts by weight, and more preferably 3 parts by weight to 100 parts by weight of the total amount of the acrylic polymer. 9.5 parts by weight. The content ratio of the above-mentioned hydroxyl group-containing monomer is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, and more preferably 3 parts by weight relative to 100 parts by weight of the total amount of the acrylic polymer parts to 9.5 parts by weight.

As the above-mentioned rubber-based adhesive, for example, rubber-based adhesives containing the following as a base polymer: natural rubber; polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene Diene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, styrene-ethylene-butylene Styrene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, recycled rubber, butyl Synthetic rubber such as base rubber, polyisobutylene, modified products of these, etc.

The gas generated from the gas generating layer is preferably a hydrocarbon (preferably aliphatic hydrocarbon)-based gas. The gas generating layer capable of generating hydrocarbon-based gas is composed of, for example, a hydrocarbon-based compound as a main component. The gas generating layer preferably contains no halogen-containing compound. If the generated gas is a hydrocarbon-based gas, the corrosion of the electronic parts as the workpiece can be prevented. This effect becomes more pronounced by forming a gas generating layer that does not contain a compound containing a halogen element. The amount of ions generated from the gas generating layer is preferably 10 m/z to 800 m/z, more preferably 11 m/z to 700 m/z, further preferably 12 m/z to 500 m/z, especially Preferably, it is 13 m/z to 400 m/z.

The above-mentioned adhesive A may contain any appropriate additives as needed. Examples of such additives include crosslinking agents, adhesion imparting agents (for example, rosin-based adhesion imparting agents, terpene-based adhesion imparting agents, hydrocarbon-based adhesion imparting agents, etc.), plasticizers (for example, trimellitic acid) Ester plasticizer, pyromellitic acid ester plasticizer), pigment, dye, anti-aging agent, conductive material, antistatic agent, light stabilizer, peeling regulator, softener, surfactant, flame retardant agents, antioxidants, etc.

As said crosslinking agent, for example, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a melamine type crosslinking agent, a peroxide type crosslinking agent, a urea type crosslinking agent, a metal alkoxide type crosslinking agent are mentioned, for example Cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, oxazoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking agent agent, etc. Among them, an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent is preferred.

Specific examples of the above-mentioned isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophor Alicyclic isocyanates such as Erone diisocyanate; Aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; Trimethylolpropane/toluene diisocyanate Isocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "" Isocyanate adducts such as Coronate HL") and isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "Coronate HX"). The content of the isocyanate-based crosslinking agent can be set to any appropriate amount according to the required adhesive force, and is typically 0.1 to 20 parts by weight, more preferably 0.5 parts by weight, relative to 100 parts by weight of the base polymer. ~10 parts by weight.

As said epoxy type crosslinking agent, for example, N,N,N',N'-tetraglycidyl m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N- Glycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C"), 1,6-hexanediol diglycidyl ether (manufactured by Kyeisha Chemical Co., Ltd., trade name "Epolight 1600" ”), neopentyl glycol diglycidyl ether (manufactured by Kyeisha Chemical Co., Ltd., trade name “Epolight 1500NP”), ethylene glycol diglycidyl ether (manufactured by Kyeisha Chemical Co., Ltd., trade name “Epolight 40E”), Propylene glycol diglycidyl ether (manufactured by Kyeisha Chemical Co., Ltd., trade name "Epolight 70P"), polyethylene glycol diglycidyl ether (manufactured by NOF Corporation, trade name "EPIOL E-400"), polypropylene glycol diglycidyl Ether (manufactured by NOF Corporation, trade name "EPIOL P-200"), sorbitol polyglycidyl ether (manufactured by Nagase chemteX, trade name "Denacol EX-611"), glycerol polyglycidyl ether (manufactured by Nagase chemteX, trade name "Denacol EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX, trade name "Denacol EX-512"), sorbitan polyglycidyl ether, trimethylol Propane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl tris(2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol -S-diglycidyl ether, an epoxy resin having two or more epoxy groups in the molecule, and the like. The content of the epoxy-based crosslinking agent can be set to any appropriate amount according to the required adhesive force, and is typically 0.01 to 10 parts by weight, more preferably 0.03 parts by weight, relative to 100 parts by weight of the base polymer. parts to 5 parts by weight.

C. Adhesive Layer The above-mentioned adhesive layer contains any appropriate adhesive B. As the adhesive B, the pressure-sensitive adhesive B1 may be used, or the curable adhesive B2 may be used.

The thickness of the above-mentioned adhesive layer is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 40 μm, further preferably 1 μm to 30 μm, particularly preferably 2 μm to 20 μm. Within such a range, an adhesive layer having favorable adhesive force and functioning well as a gas barrier layer can be formed.

The water vapor transmission rate of the above-mentioned adhesive layer is preferably 20000 g/(m ² ·day) or less, more preferably 10000 g/(m ² ·day) or less, and still more preferably 7000 g/(m ² ·day) or less, more preferably 5000 g/(m ² ·day) or less, more preferably 4800 g/(m ² ·day) or less, and most preferably 4500 g/(m ² ·day) or less. Within such a range, the adhesive layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed. When such an adhesive sheet is used, a small to-be-adhered body (for example, an electronic component) can be peeled off with high precision. The water vapor transmission rate of the adhesive layer is preferably as small as possible, and the lower limit is, for example, 100 g/(m ² ·day).

The puncture strength of the above-mentioned adhesive layer is preferably 10 mN to 3000 mN, more preferably 30 mN to 2500 mN, further preferably 50 mN to 2000 mN, and particularly preferably 100 mN to 2000 mN. Within such a range, the adhesive layer functions well as a gas barrier layer, and the shape change due to the generation of gas preferably occurs, and as a result, a deformed portion having an excellent shape is formed. When such an adhesive sheet is used, a small to-be-adhered body (for example, an electronic component) can be peeled off with high precision.

The ultraviolet transmittance of the above-mentioned adhesive layer with a wavelength of 360 nm is preferably 50% to 100%, more preferably 60% to 95%.

C-1. Pressure Sensitive Adhesive B1 Examples of the pressure-sensitive adhesive B1 include acrylic adhesives, rubber-based adhesives, vinyl alkyl ether-based adhesives, silicone-based adhesives, polyester-based adhesives, and polyamide-based adhesives. , Urethane based adhesives, styrene-diene block copolymer based adhesives, etc. Among them, an acrylic adhesive or a rubber-based adhesive is preferable, and an acrylic adhesive is more preferable. As the adhesive B1 contained in the pressure-sensitive adhesive-containing adhesive layer, the adhesive described in Section B-2 can be used.

C-2. Hardening adhesive B2 As a hardening type adhesive agent B2, a thermosetting type adhesive agent, an active energy ray hardening type adhesive agent, etc. are mentioned, for example. It is preferable to use an active energy ray hardening type adhesive. The said adhesive agent layer formed by this active energy ray hardening type adhesive agent is an adhesive agent layer formed by irradiating an active energy ray, that is, it is an adhesive agent layer which has specific adhesive force after active energy ray irradiation.

Examples of the resin material constituting the above-mentioned active energy ray-curable adhesive include: ultraviolet curing system (by Kiyomi Kato, published by the General Technology Center (1989)), photocuring technology (edited by the Technical Information Association (2000)), The resin material described in Japanese Patent Laid-Open No. 2003-292916, Japanese Patent No. 4151850 and the like. More specifically, the resin material (B2-1) containing the polymer and the active energy ray-reactive compound (monomer or oligomer) serving as the mother agent, and the resin material containing the active energy ray-reactive polymer can be exemplified. (B2-2) and so on.

Examples of the polymer to be used as the above-mentioned master batch include natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, reclaimed rubber, butyl Rubber, polyisobutylene rubber, nitrile rubber (NBR (Nitrile Butadiene Rubber)) and other rubber-based polymers; silicone-based polymers; acrylic polymers, etc. These polymers can be used alone or in combination of two or more.

Examples of the active energy ray-reactive compound include photoreactive compounds containing a plurality of functional groups having carbon-carbon multiple bonds, such as acryl, methacryloyl, vinyl, allyl, and ethynyl groups. Monomer or oligomer. Among them, a compound having an ethylenically unsaturated functional group is preferably used, and a (meth)acrylic compound having an ethylenically unsaturated functional group is more preferably used. A compound having an ethylenically unsaturated functional group easily generates radicals by ultraviolet rays, so if this compound is used, an adhesive layer that can be cured in a short time can be formed. Moreover, if the (meth)acrylic-type compound which has an ethylenically unsaturated functional group is used, the adhesive layer which has moderate hardness after hardening can be formed. Specific examples of the photoreactive monomer or oligomer include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate ) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, (meth)acryloyl group-containing compounds such as 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and (meth)acrylate urethane-based compounds ; The (meth)acryloyl group-containing compound dimer to pentamer and the like. These compounds may be used alone or in combination of two or more.

Further, as the above-mentioned active energy ray-reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, vinylsiloxane, etc., or oligomers composed of these monomers can be used. The resin material (B2-1) containing these compounds can be cured by high-energy rays such as ultraviolet rays and electron beams.

Furthermore, as the above-mentioned active energy ray-reactive compound, a mixture of organic salts such as onium salts and a compound having a plurality of heterocycles in the molecule can be used. When the mixture is irradiated with active energy rays (eg, ultraviolet rays, electron beams), the organic salts are cleaved to generate ions, which become the starting species to initiate the ring-opening reaction of the heterocyclic ring, thereby forming a three-dimensional network structure. As said organic salts, an iodonium salt, a phosphonium salt, an antimony salt, a pernium salt, a borate etc. are mentioned, for example. As a heterocycle in the compound which has a plurality of heterocycles in the said molecule|numerator, ethylene oxide, oxetane, oxolane, ethylene sulfide, aziridine, etc. are mentioned.

In the resin material (B2-1) containing the polymer serving as the base agent and the active energy ray-reactive compound, the content ratio of the active energy ray-reactive compound is preferably 0.1 with respect to 100 parts by weight of the polymer serving as the master agent. Part by weight to 500 parts by weight, more preferably 1 part by weight to 300 parts by weight, and still more preferably 10 parts by weight to 200 parts by weight.

As the active energy ray-reactive polymer, for example, one containing an active energy ray-reactive functional group having a carbon-carbon multiple bond, such as acryl group, methacryl group, vinyl group, allyl group, and ethynyl group, can be mentioned. polymer. It is preferable to use a compound (polymer) having an ethylenically unsaturated functional group, and it is more preferable to use a (meth)acrylic polymer having an acryl group or a methacryl group. As a specific example of the polymer which has an active energy ray-reactive functional group, the polymer etc. which contain polyfunctional (meth)acrylate are mentioned. The polymer containing polyfunctional (meth)acrylate preferably has an alkyl ester with a carbon number of 4 or more in the side chain, more preferably an alkyl ester with a carbon number of 6 or more, and more preferably has a carbon number of 6 or more. The alkyl ester having 8 or more carbon atoms is preferably an alkyl ester having 8 to 20 carbon atoms, and most preferably an alkyl ester having 8 to 18 carbon atoms.

The resin material (B2-2) containing the above-mentioned active energy ray-reactive polymer may further contain the above-mentioned active energy ray-reactive compound (monomer or oligomer).

The said active energy ray hardening-type adhesive agent can harden|cure by irradiation of an active energy ray. In the adhesive sheet of the present invention, after the adherend is attached before the adhesive is hardened, the adherend is irradiated with active energy rays to harden the adhesive, thereby making the adherend adhere. Examples of active energy rays include gamma rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio frequency waves, alpha rays, beta rays, electron beams, plasma currents, ionizing radiation, particle beams, and the like. Conditions such as the wavelength of the active energy ray, the irradiation dose, etc., can be set to any appropriate conditions according to the type of the resin material used, and the like. For example, the adhesive can be cured by irradiating ultraviolet rays with an irradiation dose of 10 to 1000 mJ/cm ² .

D. Intermediate layer As the form of the above-mentioned intermediate layer, for example, a resin layer, a layer having adhesiveness, etc. may be mentioned.

In one embodiment, the intermediate layer contains a thermoplastic resin. Such an intermediate layer may be a resin film containing a thermoplastic resin, a layer containing an adhesive C containing a thermoplastic resin, or the like. In another embodiment, the said intermediate layer contains curable resin (for example, ultraviolet curable resin, thermosetting resin). Such an intermediate layer may be a resin film containing a curable resin, a layer containing a curable adhesive D, or the like.

The thickness of the intermediate layer is preferably 0.1 μm to 50 μm, more preferably 1 μm to 40 μm, and still more preferably 1.5 μm to 30 μm. Within such a range, an intermediate layer that functions well as a gas barrier layer can be formed.

The water vapor transmission rate of the above-mentioned intermediate layer is preferably 5000 g/(m ² ·day) or less, more preferably 4800 g/(m ² ·day) or less, still more preferably 4500 g/(m ² ·day) or less , and more preferably 4200 g/(m ² ·day) or less. Within such a range, the intermediate layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed. When such an adhesive sheet is used, a small to-be-adhered body (for example, an electronic component) can be peeled off with high precision. The water vapor transmission rate of the intermediate layer is preferably as small as possible, and the lower limit is, for example, 0.1 g/(m ² ·day).

The puncture strength of the above-mentioned intermediate layer is preferably 300 mN to 5000 mN, more preferably 500 mN to 4500 mN, and still more preferably 1000 mN to 4000 mN. Within such a range, the intermediate layer functions well as a gas barrier layer, and a shape change due to gas generation is preferably generated, and as a result, a deformed portion having an excellent shape is formed. When such an adhesive sheet is used, a small to-be-adhered body (for example, an electronic component) can be peeled off with high precision.

The ultraviolet transmittance of the above-mentioned intermediate layer with a wavelength of 360 nm is preferably 50% to 100%, more preferably 60% to 95%.

D-1. As the intermediate layer of the resin layer The intermediate layer as the resin layer is formed of, for example, a resin film. Examples of the resin forming the resin film include polyethylene terephthalate-based resins, polyolefin-based resins, styrene-based elastomer resins (for example, SEBS, etc.), ultraviolet curable resins, thermosetting resins, amines Carbamate-based resin, epoxy-based resin, etc. In one embodiment, the resin film includes a thermoplastic resin.

The thickness of the resin film is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 30 μm, and still more preferably 1 μm to 20 μm.

D-2. An intermediate layer as an adhesive layer As an intermediate layer as an adhesive layer, an intermediate layer containing a pressure-sensitive adhesive, an intermediate layer containing a curable adhesive, and the like may, for example, be mentioned. It is preferable to arrange|position the intermediate layer containing the hardening adhesive D. In particular, if the adhesive layer containing the pressure-sensitive adhesive A and the intermediate layer containing the curable adhesive D are combined as the adhesive layer, an adhesive sheet that can form a better deformed part by laser light irradiation can be obtained. . As the hardening adhesive D, the adhesive described in the item C-2 can be used.

The thickness of the intermediate layer as an adhesive layer is preferably 5 μm to 50 μm, more preferably 5 μm to 30 μm.

E. Manufacturing Method of Adhesive Sheet The adhesive sheet of the present invention can be manufactured by any appropriate method. The adhesive sheet of the present invention may be, for example, a method of directly coating a gas-generating layer-forming composition containing the adhesive A and an ultraviolet absorber on a specific substrate to form a gas-generating layer; The adhesive layer-forming composition containing the adhesive B is applied on the layer to form an adhesive layer. In one embodiment, when the adhesive sheet has an intermediate layer, before forming the adhesive layer, the composition for forming an intermediate layer is coated on the gas generating layer to form an intermediate layer, and the intermediate layer is coated The composition for forming a cloth adhesive layer forms an adhesive layer. Moreover, after forming each layer separately, you may bond and form an adhesive sheet.

As a coating method of the above-mentioned composition, any appropriate coating method can be adopted. For example, each layer can be formed by drying after coating. As a coating method, the coating method using a multi-roll coater, a die coater, a gravure coater, an applicator, etc. is mentioned, for example. As a drying method, natural drying, heat drying, etc. are mentioned, for example. In the case of heating and drying, the heating temperature can be set to any appropriate temperature according to the properties of the substance to be dried. Moreover, active energy ray irradiation (for example, ultraviolet irradiation) can be performed according to the form of each layer.

F. Processing method of electronic parts The processing method of electronic parts of the present invention includes: attaching electronic parts to the above-mentioned adhesive sheet; and irradiating the adhesive sheet with laser light to peel off the electronic parts from the adhesive sheet. As an electronic component, a semiconductor wafer, LED (Light-emitting diode, light-emitting diode) wafer, MLCC (Multi-layer Ceramic Capacitor, multilayer ceramic capacitor) etc. are mentioned, for example.

The peeling of the above-mentioned electronic components can be carried out selectively. Specifically, by attaching and fixing a plurality of electronic components to the adhesive sheet, the electronic components can be peeled off in such a way that a part of the electronic components is peeled off, and other electronic components are kept fixed.

In one embodiment, the processing method of an electronic component of the present invention includes: performing specific processing on the electronic component after the electronic component is attached to the adhesive sheet and before the electronic component is peeled off from the adhesive sheet. The above-mentioned treatment is not particularly limited, and examples include: grinding, cutting, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, product inspection, cleaning, transfer, alignment, repair, and installation Surface protection, etc.

The size (area of the attached surface) of the electronic component is, for example, 1 μm ² to 250000 μm ² . In one embodiment, an electronic component having a size (area of an attached surface) of 1 μm ² to 6400 μm ² can be supplied for processing. In other embodiments, electronic components whose size (area of the attached surface) is 1 μm ² to 2500 μm ² can be supplied to the processing.

In one embodiment, a plurality of electronic components may be arranged on the adhesive sheet as described above. The interval between electronic components is, for example, 1 μm to 500 μm. In the present invention, it is advantageous in that the object to be processed can be temporarily fixed with a narrow interval.

As the laser light, for example, UV laser light can be used. The irradiation power of the laser light is, for example, 1 μJ to 1000 μJ. The wavelength of UV laser light is, for example, 240 nm to 380 nm.

In one embodiment, the processing method of the electronic component includes: after the electronic component is peeled off, disposing the electronic component on another sheet (eg, an adhesive sheet, a substrate, etc.). Example

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples. The evaluation methods in the examples are as follows. In addition, in the following evaluation, the adhesive sheet after peeling a separator was used. In addition, in the Examples, unless otherwise specified, "parts" and "%" are on the basis of weight.

之UV雷射光，以0.80 mW功率、40 kHz頻率進行脈衝掃描，而使氣體自氣體產生層產生。對於與脈衝掃描過之任意1點對應之黏著劑層表面(實施例1及比較例1中為氣體產生層表面)，於雷射光照射結束24小時後，利用共聚聚焦雷射顯微鏡進行觀察，而測定垂直位移Y與水平位移X(直徑；半峰全幅值)。 於位移Y為8 μm以上之情形時，剝離性顯著優異(表中，◎)；於位移Y為0.6 μm以上且未達8 μm之情形時，剝離性良好(表中，〇)；於位移Y未達0.6 μm之情形時，剝離性不充分(表中，×)。 (9)霧度值 於具有中間層之黏著片材之情形時，將剝離襯墊剝離後設置於霧度計，使入射光向樣品垂直地入射而測定霧度值。於僅由黏著層構成之黏著片材之情形時，於保留單側之剝離襯墊之狀態下設置於霧度計而進行測定，其後測定剝離襯墊單獨體之霧度值，藉由進行減法運算而獲得黏著層單獨體之霧度值。 於霧度值為20%以下之情形時，評價為被黏著體視認性：良(表中，〇)，於霧度值為20%以上50%以下之情形時，評價為被黏著體視認性：可(表中，△)，於霧度值為50%以上之情形時，評價為被黏著視認性：差(表中，×)。 (10)黏著力(氣體產生層側) 於黏著片材之黏著劑層側貼合PET#25而獲得測定樣品。對於測定樣品之氣體產生層側相對於SUS430之黏著力，藉由依照JIS Z 0237：2000之方法(貼合條件：2 kg輥1個往返，拉伸速度：300 mm/min，剝離角度180°)進行測定。 (11)黏著力(黏著劑層) 於黏著片材之氣體產生層側貼合PET#25而獲得測定樣品。對於測定樣品之黏著劑層側相對於SUS430之黏著力，藉由依照JIS Z 0237：2000之方法(貼合條件：2 kg輥1個往返，拉伸速度：300 mm/min，剝離角度180°)進行測定。 (12)變形之面內均一性 以上述(8)之方式對氣體產生層照射UV雷射光。 利用顯微鏡對隨機選擇之2 mm×2 mm範圍之變形部進行觀察，於凸部之90個%以上為相同尺寸之情形時設為良(表中，〇)，於凸部之80個%以上且未達90個%為相同尺寸之情形時設為可(表中，△)，於凸部之未達80個%為相同尺寸之情形時設為差(表中，×)。所謂相同尺寸係指位移X之差在±20%以內。 (13)變形之位置選擇性 以上述(8)之方式對氣體產生層照射UV雷射光。 將僅雷射光照射部單獨變形之情形設為合格(〇)，將於雷射照射部周邊亦有複數處變形之情形設為不合格(×)。 (14)彈性模數 使用奈米壓痕儀(Hysitron Inc公司製造之Triboindenter TI-950)，藉由在特定溫度(25℃)之單一壓入法，於壓入速度約500 nm/sec、拔出速度約500 nm/sec、壓入深度約1500 nm之測定條件下測定彈性模數。 (1) Transmittance In the case of an adhesive sheet with an intermediate layer, set the adhesive sheet on a spectrophotometer (trade name "UV-VIS Ultraviolet-Vis Spectrophotometer SolidSpec3700", manufactured by Shimadzu Corporation), and let incident light The sample was vertically incident on the gas barrier layer side, and the transmittance in the wavelength region of 300 nm to 800 nm was measured. The transmittance at the wavelengths of 360 nm and 500 nm of the transmission spectrum obtained by sampling. In the case of an adhesive sheet composed of only an adhesive layer, the measurement was performed by setting the spectrophotometer with the release liner on one side left, and then measuring the transmission spectrum of the release liner alone by performing the measurement. Subtraction is used to obtain the transmission spectrum of the adhesive layer alone. The transmittance at the wavelengths of 360 nm and 500 nm of the transmission spectrum obtained by sampling. (2) Maximum gas generation peak temperature About 0.5 mg of the adhesive sheet sample was set in a heating furnace type pyrolyzer, and a mass chromatogram was obtained by EGA-MS analysis of mass analysis of components volatilized by heating. The temperature was raised from 40°C to 500°C at a heating rate of 10°C/min using a furnace-type pyrolyzer (manufactured by Frontier Laboratories, trade name "PY2020iD"), using GC/MS (Gas chromatography/mass spectrometry, gas chromatography mass spectrometry ) analyzer (manufactured by JEOL, trade name "JMS-T100GCV"), and calculated the maximum gas generation peak temperature from the mass chromatogram in the mass range m/z=10 to 800. (3) Evaporation initiation temperature The pressure-sensitive adhesive sheet was heated in the same manner as in (2) above, and the gas generation elevation temperature calculated by EGA analysis was taken as the vaporization initiation temperature. The gas generation rise temperature is defined as the temperature at which the half value of the maximum gas generation peak of the EGA/MS chromatogram obtained according to the EGA analysis is reached. (4) Generation of gas species The adhesive sheet sample was set in an automatic sample combustion apparatus (manufactured by Mitsubishi Chemical Analytical Technologies, trade name "AQF-2100H"), and the gas generated by heating at 400°C for 30 minutes was captured. The generated gas species is identified by analyzing the captured liquid by ion chromatography. (5) 5% weight loss temperature Using a differential thermal analyzer (manufactured by TA Instruments, trade name "Discovery TGA"), the flow rate was set to 25 ml/min at a heating temperature of 10°C/min under _N2 atmosphere, and the The temperature at which the weight of the adhesive sheet is reduced by 5% is measured. (6) 10% weight reduction temperature Using a differential thermal analyzer (manufactured by TA Instruments, trade name "Discovery TGA"), the flow rate was set to 25 ml/min at a heating temperature of 10°C/min under _N2 atmosphere, and the The temperature at which the weight of the adhesive sheet is reduced by 10% is measured. The 10% weight reduction temperature was measured for the adhesive sheet and the gas generating layer (UV absorber), respectively. (7) Water Vapor Transmission Rate The sample was attached so as to cover the opening of an Al jig having an opening of 10 mm×10 mm to prepare a measurement sample, and the measurement sample was set in a water vapor transmission rate measuring device (MOCON). Between the first chamber and the second chamber of the company's product, trade name "PERMATRAN-W3/34G"), the MOCON measurement method was used for evaluation. The temperature and humidity conditions were set to 30°C/90% RH, the gas (steam) flow rate was set to 10.0±0.5 cc/min, and the measurement time was set to 20 hours. The water vapor transmission rate was measured for the adhesive sheet, the adhesive layer, and the intermediate layer, respectively. (8) The surface shape is changed to the gas generating layer side of the adhesive sheet (the side opposite to the adhesive layer) and a glass plate (manufactured by Songbo Glass Co., Ltd., large glass slide S9112 (standard large white edging No.2)) A measurement sample is obtained. From the glass plate side of the sample to be measured, use a wavelength of 355 nm and a beam diameter of about 20 μm

The UV laser light is pulsed at a power of 0.80 mW and a frequency of 40 kHz, and the gas is generated from the gas generating layer. For the surface of the adhesive layer corresponding to any point scanned by the pulse (the surface of the gas generating layer in Example 1 and Comparative Example 1), 24 hours after the laser irradiation was completed, it was observed with a confocal laser microscope, and The vertical displacement Y and the horizontal displacement X (diameter; full amplitude at half maximum) were determined. When the displacement Y was 8 μm or more, the peelability was remarkably excellent (in the table, ⊚); when the displacement Y was 0.6 μm or more and less than 8 μm, the peelability was good (in the table, 0); When Y was less than 0.6 μm, the peelability was insufficient (x in the table). (9) Haze value In the case of an adhesive sheet having an intermediate layer, the release liner was peeled off, and the haze value was measured by making the incident light perpendicular to the sample and setting it in a haze meter. In the case of an adhesive sheet composed of only an adhesive layer, the measurement is performed by setting the haze meter with the release liner on one side left, and then measuring the haze value of the release liner alone by performing the measurement. Subtraction operation is used to obtain the haze value of the adhesive layer alone. When the haze value was 20% or less, it was evaluated as the visibility of the adherent body: good (in the table, 0), and when the haze value was 20% or more and 50% or less, it was evaluated as the adherend body visibility. : OK (in the table, Δ), and when the haze value was 50% or more, the adhesion visibility was evaluated: poor (in the table, ×). (10) Adhesion (gas generating layer side) PET#25 was bonded to the adhesive layer side of the adhesive sheet to obtain a measurement sample. For the measurement of the adhesion of the gas generating layer side of the sample to SUS430, by a method according to JIS Z 0237:2000 (bonding conditions: 1 reciprocation of a 2 kg roller, stretching speed: 300 mm/min, peeling angle 180° ) to measure. (11) Adhesion (adhesive layer) PET#25 was bonded to the gas generating layer side of the adhesive sheet to obtain a measurement sample. For the measurement of the adhesive force of the adhesive layer side of the sample with respect to SUS430, by a method in accordance with JIS Z 0237: 2000 (bonding conditions: 1 reciprocating roll of 2 kg, stretching speed: 300 mm/min, peeling angle 180° ) to measure. (12) In-plane uniformity of deformation The gas generating layer was irradiated with UV laser light in the manner of (8) above. A randomly selected deformed part in the range of 2 mm × 2 mm was observed with a microscope, and when 90% or more of the convex parts were the same size, it was regarded as good (in the table, 0), and when 80% or more of the convex parts were the same size And when less than 90% were the same size, it was set as acceptable (in the table, △), and when less than 80% of the convex parts were the same size, it was set as poor (in the table, x). The so-called same size means that the difference of displacement X is within ±20%. (13) Position selectivity of deformation The gas generating layer is irradiated with UV laser light in the manner of (8) above. The case where only the laser-irradiated part was deformed alone was set as pass (0), and the case where there were multiple deformations around the laser-irradiated part was set as unacceptable (x). (14) Modulus of elasticity Using a nanoindenter (Triboindenter TI-950 manufactured by Hysitron Inc), by a single indentation method at a specific temperature (25°C), the indentation speed is about 500 nm/sec, the pull The elastic modulus was measured under the measurement conditions of an exit speed of about 500 nm/sec and an indentation depth of about 1500 nm.

[Production Example 1] Preparation of the composition a for forming a gas generating layer To toluene were added 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of ethyl acrylate, 4 parts by weight of 2-hydroxyethyl acrylate, 5 parts by weight of methyl methacrylate, and peroxide as a polymerization initiator After 0.2 weight part of benzyl, it heated to 70 degreeC, and obtained the toluene solution of an acrylic copolymer (polymer A). A toluene solution of polymer A (polymer A: 100 parts by weight), 1.5 parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), an ultraviolet absorber (manufactured by BASF, trade name "Coronate L") Tinuvin 477", structure: [Chemical 1]) 20 parts by weight were mixed to prepare a composition a for forming a gas generating layer. Table 1 shows the composition of the composition a for forming a gas generating layer.

[hua 1]

[Production Example 2] Preparation of composition b for forming gas generating layer A composition b for forming a gas generating layer was prepared in the same manner as in Production Example 1, except that the blending amount of the UV absorber was 10 parts by weight. Table 1 shows the composition of the composition b for forming a gas generating layer.

[Production Example 3] Preparation of composition c for forming gas generating layer As the UV absorber, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(commercial product) was used. A composition c for forming a gas generating layer was prepared in the same manner as in Production Example 1, except that the name was "TINUVIN 460", manufactured by BASF Corporation, structure: [Chem. 2]) 10 parts by weight. Table 1 shows the composition of the composition c for forming a gas generating layer.

[hua 2]

[Production Example 4] Preparation of the composition d for forming a gas generating layer As a UV absorber, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl)-5-hydroxybenzene and [(C10-C16 (mainly C12-C13) alkoxy) methyl] oxirane reaction product (trade name "TINUVIN 400", manufactured by BASF Corporation, structure: [Chemical 3]) 20 parts by weight, in addition to A composition d for forming a gas generating layer was prepared in the same manner as in Production Example 1. Table 1 shows the composition of the composition d for forming a gas generating layer.

[hua 3]

[Production Example 5] Preparation of composition e for forming gas generating layer After adding 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of methyl acrylate, 10 parts by weight of acrylic acid, and 0.2 parts by weight of benzyl peroxide as a polymerization initiator to ethyl acetate, it was heated to 70°C Thus, an ethyl acetate solution of the acrylic copolymer (polymer B) was obtained. An ethyl acetate solution of polymer B (polymer B: 100 parts by weight), 1 part by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and an ultraviolet absorber (manufactured by BASF, Trade name "Tinuvin 477") was mixed with 20 parts by weight to prepare a composition e for forming a gas generating layer. Table 1 shows the composition of the composition e for forming a gas generating layer.

[Production Example 6] Preparation of the composition f for forming a gas generating layer After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzyl peroxide as a polymerization initiator to ethyl acetate, it was heated to 70° C. to obtain an acrylic copolymer ( Polymer C) in ethyl acetate. An ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 1 part by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and an ultraviolet absorber (manufactured by BASF, 20 parts by weight (trade name "Tinuvin 477") was mixed to prepare a composition f for forming a gas generating layer. Table 1 shows the composition of the composition f for forming a gas generating layer.

[Production Example 7] Preparation of composition g for forming gas generating layer After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzyl peroxide as a polymerization initiator to ethyl acetate, it was heated to 70° C. to obtain an acrylic copolymer ( Polymer C) in ethyl acetate. An ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 0.1 part by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), and an ultraviolet absorber (BASF The composition g for forming a gas generating layer was prepared by mixing 20 parts by weight of the company's product, trade name "Tinuvin 477". Table 1 shows the composition of the composition g for forming a gas generating layer.

[Production Example 8] Preparation of composition h for forming gas generating layer A maleic acid-modified styrene-ethylene-butene-styrene block copolymer (SEBS: styrene moiety/ethylene-butene moiety ( weight ratio) = 30/70, acid value: 10 (mg-CH ₃ ONa/g), manufactured by Asahi Kasei Chemical Co., Ltd., trade name "Tuftec M1913") 100 parts by weight, epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd. , trade name "TETRAD-C") 3 weight parts, ultraviolet absorber (manufactured by BASF, trade name "Tinuvin 477") 20 weight parts, and toluene as a solvent were mixed to prepare a composition h for forming a gas generating layer. Table 1 shows the composition of the composition h for forming a gas generating layer.

[Production Example 8'] Preparation of composition i for forming gas generating layer After adding 100 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, and 0.2 parts by weight of benzyl peroxide as a polymerization initiator to toluene, it was heated to 70° C. to obtain toluene of the acrylic copolymer (polymer D). solution. A toluene solution of polymer D (polymer D: 100 parts by weight), 0.1 part by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), and an ultraviolet absorber (manufactured by BASF Corporation) , trade name "Tinuvin 400") 20 parts by weight were mixed to prepare a composition i for forming a gas generating layer. Table 1 shows the composition of the composition i for forming a gas generating layer.

[Production Example 8″] Preparation of composition j for forming gas generating layer In the same manner as in Production Example 5, an ethyl acetate solution of the acrylic copolymer (polymer B) was obtained. An ethyl acetate solution of polymer B (polymer B: 100 parts by weight), 0.1 part by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), and an ultraviolet absorber (BASF The composition j for forming a gas generating layer was prepared by mixing 20 parts by weight of the company's product, trade name "Tinuvin 400". Table 1 shows the composition of the composition j for forming a gas generating layer.

[Production Example 8″'] Preparation of composition k for forming gas generating layer To toluene were added 50 parts by weight of butyl acrylate, 50 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, 0.1 part by weight of 2-hydroxyethyl acrylate, 0.3 part by weight of trimethylolpropane triacrylate, and as a polymerization starter After adding 0.1 part by weight of benzyl peroxide as the agent, it was heated to 70° C. to obtain an acrylic copolymer (polymer E) toluene solution. A toluene solution of polymer E (polymer E: 100 parts by weight), 0.1 part by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), and an ultraviolet absorber (manufactured by BASF Corporation) , trade name "Tinuvin 400") 20 parts by weight were mixed to prepare a composition k for forming a gas generating layer. Table 1 shows the composition of the composition k for forming a gas generating layer.

[Production Example 9] Preparation of the composition I for forming a gas generating layer As a UV absorber, 2-[5-chloro-2H-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (trade name "TINUVIN 326", manufactured by BASF Corporation was used ) 20 parts by weight, except that the composition I for forming a gas generating layer was prepared in the same manner as in Production Example 1. Table 1 shows the composition of the composition for forming a gas generating layer I.

[Production Example 10] Preparation of Composition II Containing Thermally Expandable Microspheres Without preparing the ultraviolet absorber, the blending amount of the crosslinking agent was 1.4 parts by weight, and 30 parts by weight of thermally expandable microspheres (manufactured by Matsumoto Oil Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere F-50D"), and terpene phenol-based Thermally expandable microsphere-containing composition II was prepared in the same manner as in Production Example 5, except for 10 parts by weight of an adhesion-imparting resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name "SUMILITERESIN PR51732").

[Production Example 11] Preparation of Composition III Containing Thermally Expandable Microspheres In place of 10 parts by weight of a terpene phenol-based tackifier resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name "SUMILITERESIN PR51732"), 20 parts by weight of a terpene phenol-based tackifier resin (manufactured by Yasuhara Chemical Co., Ltd., trade name "YS POLYSTER T160") was used, Except for this, a thermally expandable microsphere-containing composition III was prepared in the same manner as in Production Example 5.

[Table 1] Composition for forming gas generating layer Production Example 1 Composition a for forming gas generating layer Production Example 2 Composition b for forming gas generating layer Production Example 3 Composition c for forming gas generating layer Production Example 4 Composition d for forming gas generating layer Production Example 5 Composition e for forming gas generating layer base polymer material Acrylic Acrylic Acrylic Acrylic Acrylic polymer species polymer A polymer A polymer A polymer A polymer B cross-linking agent cross-linking agent Isocyanate series Isocyanate series Isocyanate series Isocyanate series Isocyanate series Parts of crosslinking agent Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.0) UV absorber UV absorber species (skeleton) Hydroxyphenyl tris Hydroxyphenyl tris Hydroxyphenyl tris Hydroxyphenyl tris Hydroxyphenyl tris Product name, number of copies Tinuvin477(20) Tinuvin477(10) Tinuvin460(10) Tinuvin400(20) Tinuvin477(20) Molecular weight of UV absorber 958.2 958.2 629.8 647.8 958.2 TGA10% weight reduction temperature [℃] 352.8 352.8 401.5 391.7 352.8 Maximum absorption wavelength of UV absorbers 356nm 356nm 349nm 336nm 356nm Remark Examples 1 to 5 Example 6 Example 7 Example 8 Example 9 Composition for forming gas generating layer Production Example 6 Composition f for forming gas generating layer Production Example 7 Composition g for forming gas generating layer Production Example 8 Composition h for forming gas generating layer Production Example 8' Composition i for forming a gas generating layer Production Example 8 "Composition j for forming gas generating layer Production Example 8"" Composition k for forming gas generating layer base polymer material Acrylic Acrylic SEBS Department Acrylic Acrylic Acrylic polymer species polymer C polymer C polymer D polymer B polymer E cross-linking agent cross-linking agent Isocyanate series Epoxy system Epoxy system Epoxy system Epoxy system Epoxy system Parts of crosslinking agent Coronate/L(1.0) Tetrad C(0.1) Tetrad C(3) Tetrad C(0.1) Tetrad C(0.1) Tetrad C(0.1) UV absorber UV absorber species (skeleton) Hydroxyphenyl tris Hydroxyphenyl tris Hydroxyphenyl tris Hydroxyphenyl tris Hydroxyphenyl tris Hydroxyphenyl tris Product name, number of copies Tinuvin477(20) Tinuvin477(20) Tinuvin477(20) Tinuvin400(20) Tinuvin400(20) Tinuvin400(20) Molecular weight of UV absorber 958.2 958.2 958.2 647.8 647.8 647.8 TGA10% weight reduction temperature [℃] 352.8 352.8 352.8 391.7 391.7 391.7 Maximum absorption wavelength of UV absorbers 356nm 356nm 356nm 336nm 336nm 336nm Remark Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Composition for forming gas generating layer Production Example 9 Composition I for forming a gas generating layer Production Example 10 Composition II containing thermally expandable microspheres Production Example 11 Composition III containing thermally expandable microspheres base polymer material Acrylic Acrylic Acrylic polymer species polymer A polymer A polymer A cross-linking agent cross-linking agent Isocyanate series Isocyanate series Isocyanate series Parts of crosslinking agent Coronate/L(1.5) Coronate/L(1.4) Coronate/L(1.4) UV absorber UV absorber species (skeleton) Benzotriazoles - - Product name, number of copies Tinuvin326(20) - - Molecular weight of UV absorber 315.8 - - TGA10% weight reduction temperature [℃] 234.5 - - Maximum absorption wavelength of UV absorbers 355 nm - - Remark Heat-expandable microspheres Heat-expandable microspheres Comparative Examples 1 and 2 Comparative Example 3 Comparative Example 4

[Manufacturing example 12] Preparation of adhesive a In the same manner as in Production Example 1, a toluene solution of the acrylic copolymer (polymer A) was obtained. A toluene solution of polymer A (polymer A: 100 parts by weight), 3 parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and a surfactant (manufactured by Kao, trade name) "EXCEPARL IPP") was mixed with 5 parts by weight to prepare adhesive a. The composition of the adhesive a is shown in Table 2.

[Manufacturing example 12'] Preparation of adhesive b In the same manner as in Production Example 6, a toluene solution of the acrylic copolymer (polymer C) was obtained. A toluene solution of polymer C (polymer C: 100 parts by weight), 3 parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and an epoxy-based crosslinking agent (Mitsubishi Gas Chemical) Company manufacture, brand name "TETRAD-C") 1 weight part was mixed to prepare adhesive b. The composition of the adhesive b is shown in Table 2.

[Manufacturing Example 13] Preparation of Adhesive I Adhesive I was prepared in the same manner as in Production Example 12, except that the blending amount of the crosslinking agent was 1 part by weight and the surfactant was not contained. The composition of Adhesive I is shown in Table 2.

[Table 2] adhesive composition Production Example 12 Adhesive a Production Example 12' Adhesive b Production Example 13 Adhesive I base polymer material Acrylic Acrylic Acrylic polymer species polymer A polymer C polymer A cross-linking agent cross-linking agent Isocyanate series Isocyanate series Isocyanate series Product name, number of copies Coronate/L(3) Coronate/L(3) Coronate/L(1) cross-linking agent - Epoxy system - Product name, number of copies - Tetrad C(1) - Surfactant Surfactant species Fatty acid ester system - - Product name, number of copies EXCEPARL IPP(5) - - Examples 2 to 10 Comparative Example 2 Examples 13, 14, 15 Comparative Examples 3 to 4

[Production Example 14] Preparation of the composition a for forming an intermediate layer In the same manner as in Production Example 5, an ethyl acetate solution of the acrylic copolymer (polymer B) was obtained. An ethyl acetate solution of polymer B (polymer B: 100 parts by weight), 1 part by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C"), a UV oligomer (Mitsubishi Chemical The composition a for intermediate layer formation was prepared by mixing 50 parts by weight of the company's product, trade name "violet UV-1700B", and 3 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "Omnirad 127"). The composition of the composition a for intermediate layer formation is shown in Table 3.

[Production Example 15] Preparation of composition b for intermediate layer formation Maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (SEBS: styrene moiety/ethylene-butene moiety (weight ratio) = 30/70, acid value: 10 (mg-CH ₃ ONa/g), manufactured by Asahi Kasei Chemical Co., Ltd., trade name "Tuftec M1913") 100 parts by weight, epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., Trade name "TETRAD-C") 3 parts by weight, fatty acid ester surfactant (manufactured by Kao Corporation, trade name "EXCEPARL IPP", molecular weight: 298.5, carbon number of alkyl group: 16) 3 parts by weight, and as a solvent and mixed with toluene to obtain a composition b for forming an intermediate layer. Table 3 shows the composition of the composition b for forming an intermediate layer.

[table 3] Composition for forming an intermediate layer Production Example 14 Composition a for forming an intermediate layer Production Example 15 Intermediate layer forming composition b base polymer material Acrylic SEBS Department polymer species polymer B UV oligomer UV oligomer UV curable urethane acrylate - Product name, number of copies UV-1700B(50) - cross-linking agent cross-linking agent Epoxy system Epoxy system Product name, number of copies Tetrad C(1) Tetrad C(3) photopolymerization initiator photopolymerization initiator Benzoalanone series - Product name, number of copies Irg127(3) - Example 3 Example 4

[Example 1] The composition a for forming a gas generating layer obtained in Production Example 1 was applied to a polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 7 μm. A film (manufactured by Toray Industries, Ltd., trade name "Cerapeel" thickness: 38 μm) was then dried to obtain an adhesive sheet comprising only a gas generating layer on the polyethylene terephthalate film. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 4.

[Example 2] The adhesive a obtained in Production Example 12 was applied to a polyethylene terephthalate film (thickness: 75 μm) with a silicone release agent-treated surface so that the thickness after the solvent was volatilized (dried) became 15 μm. μm), followed by drying to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition a for forming a gas generating layer obtained in Production Example 1 was applied to a polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 7 μm. A film (manufactured by Toray Industries, Ltd., trade name "Cerapeel" thickness: 38 μm) was dried to form a gas generating layer precursor layer a on the polyethylene terephthalate film. The above-mentioned adhesive layer precursor layer a and the above-mentioned gas generating layer precursor layer a are laminated between rolls and bonded to obtain a film sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. Adhesive sheet (adhesive layer/gas generating layer). The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 4.

[Example 3] The adhesive a obtained in Production Example 12 was coated on a polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 15 μm film (thickness: 75 μm), and then dried to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition a for forming an intermediate layer obtained in Production Example 14 was applied to a polyethylene terephthalate film with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 15 μm. (Made by Toray Industries, Ltd., trade name "Cerapeel" Thickness: 38 μm), after that, drying was performed to form an intermediate layer precursor layer a on the polyethylene terephthalate film. Then, the above-mentioned adhesive layer precursor layer a and the above-mentioned intermediate layer precursor layer a are laminated between rolls and bonded, and UV irradiation is performed from the intermediate layer precursor layer side under the condition of 500 mJ/cm ² to obtain a sandwiched belt. Laminate precursor layer a between polyethylene terephthalate films with silicone release agent treated surfaces. The composition a for forming a gas generating layer obtained in Production Example 1 was applied to a polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 7 μm. A film (manufactured by Toray Industries, Ltd., trade name "Cerapeel" thickness: 38 μm) was dried to form a gas generating layer precursor layer a on the polyethylene terephthalate film. After peeling off the polyethylene terephthalate film with the silicone release agent-treated surface on the intermediate layer precursor layer a side of the laminate precursor layer a, the intermediate layer precursor layer a of the laminate precursor layer a and The gas generating layer precursor layer a is laminated between rolls and bonded to obtain an adhesive sheet (adhesive layer/intermediate) sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. layer/gas generating layer). The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 4.

[Example 4] The adhesive a obtained in Production Example 12 was applied to a polyethylene terephthalate film (thickness: 75 μm) with a silicone release agent-treated surface so that the thickness after the solvent was volatilized (dried) became 15 μm. μm), followed by drying to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition b for forming an intermediate layer obtained in Production Example 15 was applied to a polyethylene terephthalate film with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 15 μm. (Made by Toray Industries, Ltd., trade name "Cerapeel" Thickness: 38 μm), after that, drying was performed to form an intermediate layer precursor layer a on the polyethylene terephthalate film. Then, the above-mentioned adhesive layer precursor layer a and the above-mentioned intermediate layer precursor layer b are laminated between rolls and bonded to obtain sandwiched between the polyethylene terephthalate films with the silicone release agent-treated surface. The laminate precursor layer b. The composition a for forming a gas generating layer obtained in Production Example 1 was applied to a polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 7 μm. A film (manufactured by Toray Industries, Ltd., trade name "Cerapeel" thickness: 38 μm) was dried to form a gas generating layer precursor layer a on the polyethylene terephthalate film. After peeling off the polyethylene terephthalate film with the silicone release agent-treated surface on the intermediate layer precursor layer b side of the laminate precursor layer b, the intermediate layer precursor layer b of the laminate precursor layer b and The gas generating layer precursor layer a is laminated between rolls and laminated to obtain an adhesive sheet (adhesive layer/intermediate) sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. layer/gas generating layer). The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 4.

[Example 5] The adhesive a obtained in Production Example 12 was applied to a polyethylene terephthalate film (thickness: 75 μm) with a silicone release agent-treated surface so that the thickness after the solvent was volatilized (dried) became 15 μm. μm), followed by drying to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition a for forming a gas generating layer obtained in Production Example 1 was applied to a polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after volatilization (drying) of the solvent was 7 μm. A film (manufactured by Toray Industries, Ltd., trade name "Cerapeel" thickness: 38 μm) was dried to form a gas generating layer precursor layer a on the polyethylene terephthalate film. The above-mentioned adhesive layer precursor layer a was laminated between rolls and attached to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Ltd., trade name "Lumirror #2F51N" thickness: 2 μm). Next, the gas generating layer precursor layer a was laminated between rolls and attached to the opposite side of the adhesive layer precursor layer a of the polyethylene terephthalate film. In this way, an adhesive sheet (adhesive layer/intermediate layer/gas generating layer) sandwiched between the polyethylene terephthalate films with the silicone release agent-treated surface was obtained. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 4.

[Example 6] An adhesive sheet was obtained in the same manner as in Example 5, except that the composition b for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 5.

[Example 7] An adhesive sheet was obtained in the same manner as in Example 5, except that the composition c for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 5.

[Example 8] An adhesive sheet was obtained in the same manner as in Example 5, except that the composition d for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 5.

[Example 9] An adhesive sheet was obtained in the same manner as in Example 5, except that the composition e for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 5.

[Example 10] An adhesive sheet was obtained in the same manner as in Example 5, except that the composition f for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 5.

[Example 11] An adhesive sheet was obtained in the same manner as in Example 1, except that the composition g for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Example 12] An adhesive sheet was obtained in the same manner as in Example 1, except that the composition h for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 adhesive layer adhesive - adhesive a adhesive a adhesive a adhesive a Thickness [μm] - 15 7 7 7 Water Vapor Transmission Rate of Adhesive Layer [g/(m ²・day)] - 3435.3 4059.3 4059.3 4059.3 middle layer Intermediate layer material - - Composition a for forming an intermediate layer Intermediate layer forming composition b PET Thickness [μm] - - 15 15 2 Water vapor transmission rate of the intermediate layer [g/(m ²・day)] - - 1778 78 1114.34 gas generating layer gas generating layer material Composition a for forming gas generating layer Composition a for forming gas generating layer Composition a for forming gas generating layer Composition a for forming gas generating layer Composition a for forming gas generating layer Thickness [μm] 7 7 7 7 7 Molecular weight of UV absorber 958.2 958.2 958.2 958.2 958.2 TGA10% weight reduction temperature [℃] 352.8 352.8 352.8 352.8 352.8 Maximum absorption wavelength of UV absorbers 356nm 356nm 356nm 356nm 356nm adhesive sheet Thickness [μm] 7 twenty two 29 29 16 gas generating properties Transmittance@360 nm[%] 0.05 0.01 0.02 0.00 0.01 Transmittance@500 nm[%] 91.78 91.98 92.62 92.76 91.98 Maximum gas production peak temperature [℃] 380 380 370 370 380 Gasification start temperature [℃] 335 335 330 330 335 gas species hydrocarbon hydrocarbon hydrocarbon hydrocarbon hydrocarbon TGA5% weight reduction temperature [℃] 310.6 312.6 306.2 304.5 312.6 TGA10% weight reduction temperature [℃] 33.5 349.5 340.1 339.5 349.5 Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 4062.6 3158.9 1238.1 198.1 334.2 surface shape change Height (Y: vertical displacement) [μm] -6.7 3.4 1.4 1.2 10.6 Diameter (X: horizontal displacement) [μm] 19.1 23.1 13.2 10.1 51.2 state cracked concave foam convex foam convex foam convex foam convex haze value 0.2 1.5 0.4 1.2 1.5 Adhesion to SUS430 [N/20 mm] (Adhesive layer side) 4.20 3.46 2.32 0.33 Adhesion to SUS430 [N/20 mm] (gas generating layer side) 6.02 5.22 3.86 2.95 4.74 stripping 〇 〇 〇 〇 ◎ In-plane uniformity of deformation 〇 〇 〇 〇 〇 clinging stereopsis 〇 〇 〇 〇 〇 location selectivity 〇 〇 〇 〇 〇

[table 5] Example 6 Example 7 Example 8 Example 9 Example 10 adhesive layer adhesive adhesive a adhesive a adhesive a adhesive a adhesive a Thickness [μm] 7 7 7 7 7 Water Vapor Transmission Rate of Adhesive Layer [g/(m ²・day)] 4059.3 4059.3 4059.3 4059.3 4059.3 middle layer Intermediate layer material PET PET PET PET PET Thickness [μm] 2 2 2 2 2 Water vapor transmission rate of the intermediate layer [g/(m ²・day)] 1114.34 1114.34 1114.34 1114.34 1114.34 gas generating layer gas generating layer material Composition b for forming gas generating layer Composition c for forming gas generating layer Composition d for forming gas generating layer Composition e for forming gas generating layer Composition f for forming gas generating layer Thickness [μm] 7 7 7 7 7 Molecular weight of UV absorber 958.2 629.8 647.8 958.2 958.2 TGA10% weight reduction temperature [℃] 352.8 401.5 391.7 352.8 352.8 Maximum absorption wavelength of UV absorbers 356nm 349nm 336nm 356nm 356nm adhesive sheet Thickness [μm] 16 16 16 16 16 gas generating properties Transmittance@360 nm[%] 0.05 0.00 0.20 0.02 0.01 Transmittance@500 nm[%] 92.2 92.10 91.93 90.24 92.17 Maximum gas production peak temperature [℃] 380 390 395 380 380 Gasification start temperature [℃] 335 360 370 335 335 gas species hydrocarbon hydrocarbon hydrocarbon hydrocarbon hydrocarbon TGA5% weight reduction temperature [℃] 310.3 319.2 326.2 313.2 309.7 TGA10% weight reduction temperature [℃] 347.2 359.6 369.9 351.4 349.7 Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 330.2 328.4 339.4 336.2 284.1 surface shape change Height (Y: vertical displacement) [μm] 5.3 10.5 4.5 6.5 15.7 Diameter (X: horizontal displacement) [μm] 42.1 40.6 41.3 39.3 41.5 state foam convex foam convex foam convex foam convex foam convex haze value 1.6 10.4 1.4 26 9 Adhesion to SUS430 [N/20 mm] (Adhesive layer side) 0.31 0.35 0.39 0.46 0.42 Adhesion to SUS430 [N/20 mm] (gas generating layer side) 4.59 4.30 4.68 2.52 6.37 stripping 〇 ◎ 〇 〇 ◎ In-plane uniformity of deformation 〇 △ 〇 △ △ clinging stereopsis 〇 〇 〇 △ 〇 location selectivity 〇 〇 〇 〇 〇

[Table 6] Example 11 Example 12 Example 13 Example 14 Example 15 adhesive layer adhesive - - adhesive b adhesive b adhesive b Thickness [μm] - - 10 10 10 Water Vapor Transmission Rate of Adhesive Layer [g/(m ²・day)] - - 3754.3 3754.3 3754.3 middle layer Intermediate layer material - - - - - Thickness [μm] - - - - - Water vapor transmission rate of the intermediate layer [g/(m ²・day)] - - - - - gas generating layer gas generating layer material Composition g for forming gas generating layer Composition h for forming gas generating layer Composition i for forming gas generating layer Composition for forming gas generating layer j Composition k for forming gas generating layer Thickness [μm] 20 20 20 20 20 Molecular weight of UV absorber 958.2 958.2 647.8 647.8 647.8 TGA10% weight reduction temperature [℃] 352.8 352.8 391.7 391.7 391.7 Maximum absorption wavelength of UV absorbers 356nm 356nm 336nm 336nm 336nm Thicknessh(gas)[μm] 20 20 20 20 20 Elastic modulus Er(gas)[MPa] 0.95 77.62 3.05 2.88 2.12 LogEr(gas) 5.98 7.89 6.48 6.46 6.33 8.01×h(gas) ^-0.116 5.66 5.66 5.66 5.66 5.66 The lower limit value of the elastic modulus of the gas generating layer calculated from Log(Er(gas)× ^{10 6} )≧8.01×h(gas) ^{- 0.116} [MPa] 0.46 0.46 0.46 0.46 0.46 7.66×h(gas) ^-0.092 5.81 5.81 5.81 5.81 5.81 The lower limit value of the elastic modulus of the gas generating layer calculated from Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^-0.092 [MPa] 0.65 0.65 0.65 0.65 0.65 7.52×h(gas) ^-0.081 5.90 5.90 5.90 5.90 5.90 The lower limit value of the elastic modulus of the gas generating layer calculated from Log(Er(gas)×10 ⁶ )≧7.52×h(gas) ^-0.081 [MPa] 0.79 0.79 0.79 0.79 0.79 47.675×h(gas) ^-0.519 10.07 10.07 10.07 10.07 10.07 Upper limit of elastic modulus of gas generating layer calculated from Log(Er(gas)×10 ⁶ )≦47.675×h(gas) ^-0.519 [MPa] 11765.71 11765.71 11,765.7 11,765.7 11,765.7 adhesive sheet Thickness [μm] 20 20 30 30 30 gas generating properties Transmittance@360 nm[%] 0.18 0.19 0.37 0.48 0.36 Transmittance@500 nm[%] 89.11 90.20 88.43 83.44 88.30 Maximum gas production peak temperature [℃] 380 380 390 395 395 Gasification start temperature [℃] 335 335 360 375 370 gas species hydrocarbon hydrocarbon hydrocarbon hydrocarbon hydrocarbon TGA5% weight reduction temperature [℃] 304.90 308.40 328.9 331.1 332.3 TGA10% weight reduction temperature [℃] 327.80 329.80 358.0 360.4 359.6 Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 3113.20 3356.80 2888.1 3001.2 2791.3 surface shape change Height (Y: vertical displacement) [μm] 0.9 0.7 2.4 1.3 1.9 Diameter (X: horizontal displacement) [μm] 12.3 14.6 26.3 25.7 22.4 state foam convex foam convex foam convex foam convex foam convex haze value 7.3 8.2 5.8 47.1 5.8 Adhesion to SUS430 [N/20 mm] (Adhesive layer side) - - 0.38 0.28 0.43 Adhesion to SUS430 [N/20 mm] (gas generating layer side) 0.40 0.21 7.50 8.72 16.20 stripping 〇 〇 〇 〇 〇 In-plane uniformity of deformation 〇 〇 〇 △ 〇 clinging stereopsis 〇 〇 〇 △ 〇 location selectivity 〇 〇 〇 〇 〇

[Comparative Example 1] An adhesive sheet was obtained in the same manner as in Example 1, except that the composition for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 7.

[Comparative Example 2] An adhesive sheet was obtained in the same manner as in Example 5, except that the composition for forming a gas generating layer was used instead of the composition a for forming a gas generating layer. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 7.

[Comparative Example 3] In place of the adhesive a, the adhesive I was used, the thickness of the adhesive layer was 10 μm, a PET film with a thickness of 188 μm was used as the intermediate layer, and the composition containing thermally expandable microspheres was used instead of the composition a for forming a gas generating layer. An adhesive sheet was obtained in the same manner as in Example 5, except that a gas generating layer of 48 μm was formed in Compound II. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 7.

[Comparative Example 4] The adhesive agent I was used instead of the adhesive agent a, the thickness of the adhesive agent layer was 10 μm, the PET film with a thickness of 100 μm was used as the intermediate layer, and the composition containing heat-expandable microspheres was used instead of the composition a for forming a gas generating layer. An adhesive sheet was obtained in the same manner as in Example 5, except that the gas generating layer of 48 μm was formed in Compound III. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (13). The results are shown in Table 7.

[Table 7] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 adhesive layer adhesive - adhesive a Adhesive I Adhesive I Thickness [μm] - 7 10 10 Water Vapor Transmission Rate of Adhesive Layer [g/(m ²・day)] - 4059.3 - - middle layer Intermediate layer material - PET PET PET Thickness [μm] - 2 188 100 Water vapor transmission rate of the intermediate layer [g/(m ²・day)] - 3450 - - gas generating layer gas generating layer material Composition I for forming gas generating layer Composition I for forming gas generating layer Composition II containing heat-expandable microspheres Composition III containing heat-expandable microspheres Thickness [μm] 7 7 48 48 Molecular weight of UV absorber 315.8 315.8 - - TGA10% weight reduction temperature [℃] 234.5 232.5 - - Maximum absorption wavelength of UV absorbers 355 nm 355 nm - - adhesive sheet Thickness [μm] 7 16 246 158 gas generating properties Transmittance@360 nm[%] 7.56 7.45 58.32 71.78 Transmittance@500 nm[%] 88.74 86.44 84.01 84.15 Maximum gas production peak temperature [℃] 250 250 - - Gasification start temperature [℃] 215 215 - - gas species Hydrocarbon halogen compound Hydrocarbon halogen compound hydrocarbon hydrocarbon TGA5% weight reduction temperature [℃] 240.6 245.6 - - TGA10% weight reduction temperature [℃] 280.3 284.3 - - Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 4062.6 298.6 - - surface shape change Height (Y: vertical displacement) [μm] -6.2 8.2 ≧100 μm ≧100 μm Diameter (X: horizontal displacement) [μm] 16.1 36.4 ≧200 μm ≧200 μm state cracked concave foam convex Plural foaming convex Plural foaming convex haze value 51.2 58.5 66.4 56.4 Adhesion to SUS430 [N/20 mm] (Adhesive layer side) 1.05 - - Adhesion to SUS430 [N/20 mm] (gas generating layer side) 0.58 0.58 - - stripping 〇 ◎ ◎ ◎ In-plane uniformity of deformation △ △ × × clinging stereopsis × × × × location selectivity 〇 〇 × ×

4: Sample 5A, 5B: Specimen holder 6: Compression testing machine 10: Gas generating layer 20: Adhesive layer 30: middle layer 100,100',200: Adhesive sheet

1(a) and (b) are schematic cross-sectional views of an adhesive sheet according to an embodiment of the present invention. 2 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention. Fig. 3 is a schematic diagram for explaining a method of measuring puncture strength.

10: Gas generating layer

20: Adhesive layer

100,100': Adhesive sheet

Claims (16)

An adhesive sheet having a gas generating layer for generating gas by irradiation with laser light, and The haze value is below 50%, The transmittance of ultraviolet rays with a wavelength of 360 nm is less than 30%. The adhesive sheet according to claim 1, wherein the thickness of the gas generating layer is 0.1 μm to 50 μm. The adhesive sheet according to claim 1 or 2, wherein the gas generating layer is an ultraviolet-absorbing layer. The adhesive sheet of claim 3, wherein the gas generating layer contains an ultraviolet absorber. For the adhesive sheet of claim 1 or 2, the transmittance of ultraviolet rays with a wavelength of 500 nm is 50% to 100%. The adhesive sheet according to claim 1 or 2, wherein the gas generating layer is a layer for generating hydrocarbon-based gas. The adhesive sheet according to claim 1 or 2, wherein the vaporization initiation temperature of the gas generating layer is 150°C to 500°C, the so-called vaporization initiation temperature of the gas generating layer refers to the vaporization initiation temperature of the adhesive sheet according to the temperature of the adhesive sheet. The rising temperature of gas generation calculated by EGA analysis, the so-called rising temperature of gas generation is defined as the temperature that reaches the half value of the maximum gas generation peak value of the released gas analysis/mass spectrometry (EGA/MS) spectrum obtained by EGA analysis . For the adhesive sheet of claim 1 or 2, the 10% weight reduction temperature is 200°C to 500°C. The so-called 10% weight reduction temperature refers to the thermogravimetric analysis (TGA analysis) when the adhesive sheet is heated up. The gas generating layer The temperature at the point in time when the weight is reduced by 10% by weight with respect to the weight before the temperature increase. The adhesive sheet according to claim 1 or 2, further comprising an adhesive layer on at least one side of the gas generating layer, and The adhesive layer is a layer whose surface is deformed by irradiating the above-mentioned adhesive sheet with laser light. The adhesive sheet according to claim 9, wherein the thickness of the adhesive layer is 0.1 μm to 50 μm. The adhesive sheet according to claim 9, wherein the adhesive layer is foamed by irradiating the adhesive sheet with laser light. A processing method for electronic parts, comprising: attaching electronic parts to the adhesive sheet according to any one of claims 1 to 11; and irradiating the adhesive sheet with laser light to peel off the electronic parts from the adhesive sheet Components. The processing method of an electronic component according to claim 12, wherein the above-mentioned peeling of the electronic component is performed at selected locations. The processing method for electronic parts as claimed in claim 12 or 13, which includes: After attaching the electronic component to the adhesive sheet and before peeling the electronic component from the adhesive sheet, Perform specific processing on the electronic part. The method for processing electronic parts according to claim 14, wherein the above-mentioned processing is grinding, cutting, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, product inspection, cleaning, transfer printing, alignment, Repair or device surface protection. The method for processing electronic parts according to claim 12 or 13, comprising: after peeling the electronic parts from the adhesive sheet, disposing the electronic parts on another sheet.

Images