TWI824455B - adhesive sheet - Google Patents

Abstract

The present invention provides an adhesive sheet that can temporarily fix small electronic components (for example, a chip with a size of 100 μm□ or less) well and can be peeled off well. The adhesive sheet of the present invention includes a gas generating layer and at least one adhesive layer disposed on one side of the gas generating layer. The adhesive layer is a layer that is deformed by irradiating the adhesive sheet with laser light. In one embodiment, the gas generating layer is a layer that can absorb ultraviolet rays.

Description

adhesive sheet

The present invention relates to an adhesive sheet.

Previously, when electronic parts were processed (processed), there were cases where the object to be processed was temporarily fixed on an adhesive sheet during processing, and the object to be processed was peeled off from the adhesive sheet after processing. . As an adhesive sheet used in such an operation, there are cases where an adhesive sheet is used that has a specific adhesive force during processing and that can be reduced in adhesive force after processing. As one such adhesive sheet, an adhesive sheet containing heat-expandable microspheres in an adhesive layer has been proposed (for example, Patent Document 1). The adhesive sheet containing thermally expandable microspheres has the following characteristics: It has a specific adhesive force, and by using heat to expand the thermally expandable microspheres, unevenness is formed on the adhesive surface, thereby reducing the contact area and thus reducing the adhesive force. or disappear. This kind of adhesive sheet has the advantage that the object to be processed can be easily peeled off without external stress.

However, in recent years, as various devices have become lighter and the number of devices mounted on them has increased, the miniaturization of electronic components has been promoted, resulting in the need to temporarily fix the electronic components that have been miniaturized to a size similar to that of the thermally expandable microspheres. . When electronic parts that have been miniaturized are temporarily fixed and processed, the influence of particle size deviation becomes greater, such as the presence of thermally expandable microspheres with larger particle diameters and the areas where thermally expandable microspheres do not exist. There may be situations where good peeling cannot be performed in this area. Prior technical literature patent documents

Patent Document 1: Japanese Patent Application Publication No. 2001-131507

[Problem to be solved by the invention]

The present invention was made to solve the above-mentioned previous problems, and its object is to provide an adhesive sheet that can temporarily fix small electronic components (for example, a chip with a size of 100 μm□ or less) well and can be peeled off well. [Technical means to solve problems]

The adhesive sheet of the present invention is provided with a gas generating layer and at least one adhesive layer disposed on one side of the gas generating layer. The adhesive layer is a layer whose surface is deformed by irradiating the adhesive sheet with laser light. . 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 thickness of the gas generating layer ranges from 0.1 μm to 50 μm. In one embodiment, the gas generating layer is a layer that generates hydrocarbon gas. In one embodiment, the gasification starting temperature of the gas generating layer is 150°C to 500°C. In one embodiment, the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] of the gas generation layer obtained by the nanoindentation method satisfy the following formula (1). Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^-0.116・・・(1) In one embodiment, the thickness of the adhesive layer is 0.1 μm˜50 μm. In one embodiment, the deformation amount of the surface of the adhesive layer caused by irradiating the adhesive sheet with laser light is 0.6 μm or more in terms of the vertical displacement of the adhesive layer. In one embodiment, the ultraviolet transmittance of the above-mentioned adhesive sheet at a wavelength of 360 nm is 30% or less. In one embodiment, the 10% weight loss temperature of the adhesive sheet is 200°C to 500°C. In one embodiment, the water vapor transmission rate of the above-mentioned adhesive sheet is 5000 g/(m ² ·day) or less. According to other aspects of the present invention, a method for processing electronic components is provided. The processing method of the electronic components includes: attaching the electronic components to the adhesive sheet; and irradiating the adhesive sheet with laser light to peel off the electronic components from the adhesive sheet. In one embodiment, the electronic components are peeled off at selected locations. In one embodiment, the method includes: performing specific processing on the electronic component after attaching the electronic component to the adhesive sheet and before peeling off the electronic component from the adhesive sheet. In one embodiment, the above-mentioned processing is grinding, cutting, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer, alignment, repair or device surface protection. In one embodiment, the processing method of the electronic components includes: peeling off the electronic components from the adhesive sheet, and arranging the electronic components on another sheet. [Effects of the invention]

According to the present invention, it is possible to provide an adhesive sheet that can temporarily fix small electronic components (for example, a chip with a size of 100 μm□ or less) well and can be peeled off well.

A. Overview of Adhesive Sheet Figure 1 is a schematic cross-sectional view of an adhesive sheet according to a preferred embodiment of the present invention. The adhesive sheet 100 includes a gas generating layer 10 and at least one adhesive layer 20 arranged on one side of 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 using laser light irradiation. The surface of the adhesive layer 20 is deformed by irradiating the adhesive sheet (essentially a gas generating layer) with laser light. In one embodiment, the deformation occurs on the side of the adhesive layer 20 opposite to the gas generating layer 10 due to the gas generated from the gas generating layer 10 . As the laser light, UV (ultraviolet, ultraviolet) laser light is typically used.

The adhesive sheet of the present invention can be used by attaching an object to be processed such as electronic components to an adhesive layer. The adhesive sheet of the present invention is provided with a gas generating layer, which generates gas locally in a small range by irradiation with laser light. As described above, the generation of this gas deforms the adhesive layer, and as a result, the portion irradiated with laser light exhibits peelability. Typically, the laser light is irradiated from the side of the gas generation layer opposite to the adhesive layer. According to the present invention, deformation can be generated in a micro range in the manner described above, so that when extremely fine small electronic components are processed (processed), the small electronic components can be peeled off satisfactorily. Furthermore, even when small electronic components that need to be peeled off are temporarily fixed adjacent to small electronic components that do not need to be peeled off, it is possible to peel off the parts to be peeled off and not to peel off parts other than the parts to be peeled off. It can only peel off small electronic parts that need to be peeled off, and can also prevent unnecessary detachment of small electronic parts. In order to cause the deformation of the adhesive layer to occur satisfactorily, it is preferable to block at least part of the gas generated above in such a manner that it does not escape from the adhesive sheet. The adhesive layer can function as a gas barrier layer. In addition, the adhesive sheet has excellent directivity when peeled off and can be peeled off only at a desired location. It is also advantageous in terms of preventing breakage and reducing paste residue. Furthermore, the directivity during peeling is an index indicating the positional accuracy when an adherend such as a small electronic component is peeled off from the adhesive sheet and is aimed at a certain distance away from the adhesive sheet and ejected. If the directivity is excellent, then Prevent the adherend from flying out in unexpected directions during peeling.

The so-called deformation of the adhesive layer refers to the displacement in the normal direction (thickness direction) and horizontal direction (the direction orthogonal to the thickness direction) of the adhesive layer. The deformation of the adhesive layer is produced, for example, in the following way: by using a wavelength of 355 nm and a beam diameter of approximately 20 μm. The UV laser light is pulse scanned at a power of 0.80 mW and a frequency of 40 kHz to generate gas from the gas generation layer. Regarding the deformed shape, for example, any point that has been pulse scanned is observed by measurement using a confocal laser microscope or a non-contact interference microscope (WYKO) one minute after the laser light irradiation is completed. The shape may be foamed (convex), through-holes (concave-convex), or recessed (concave), and peelability can be generated by these deformations. When it is necessary to efficiently peel off electronic components along the normal direction, it is preferable that the displacement in the normal direction before and after laser light irradiation changes greatly, especially for forming a foamed shape. Foaming (convex shape) is based on the surface of the adhesive sheet of the unirradiated part, the highest point is defined as the vertical displacement Y, and the full amplitude at half maximum is defined as the horizontal displacement X (diameter). Regarding the through-holes (concave-convex) and depressions (concave) formed after laser light 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 part deformed by laser light irradiation will also be referred to as the "deformation part". The vertical displacement of the adhesive layer is preferably 0.6 μm or more, more preferably 0.7 μm or more, and further preferably 1.0 μm or more. If it is within this range, the releasability will be excellent and the directivity during peeling will be excellent. In addition, it can be peeled off in the desired direction with high precision, and as a result, paste residue, damage, etc. can be prevented. The upper limit of the vertical displacement is, for example, 10 μm (preferably 20 μm). The horizontal displacement of the adhesive layer is preferably 80 μm or less, more preferably 50 μm or less, and further preferably 40 μm or less. If it is within this range, peeling of only the necessary parts can be preferably performed on a smaller adherend. In addition, the same effect can be expected when the adherends are arranged at narrow intervals. The lower limit of the horizontal displacement is, for example, 3 μm (preferably 4 μm).

FIG. 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 an intermediate layer, the deformation of the adhesive layer can be easily controlled (details will be described later). In addition, the intermediate layer can cooperate with the adhesive layer to function as a gas barrier layer. Therefore, by providing the intermediate layer, the gas barrier properties will be improved, and an adhesive sheet with better deformation of the adhesive layer can be obtained. The middle layer can be a single layer or multiple layers.

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

The adhesive force of the adhesive layer of the adhesive sheet of the present invention relative to SUS430 is preferably 0.1 N/20 mm or more, more preferably 0.2 N/20 mm to 50 N/20 mm, and further preferably 0.5 N/20 mm. ~40 N/20 mm, especially 0.7 N/20 mm ~ 20 N/20 mm, the best is 1 N/20 mm ~ 10 N/20 mm. If it is within this range, it is possible to obtain an adhesive sheet that exhibits good adhesiveness as a temporary fixing sheet used in the manufacture of electronic components, for example. In this manual, the so-called adhesion refers to the method in accordance with JIS (Japanese Industrial Standards, Japanese Industrial Standards) Z 0237: 2000 in an environment of 23°C (laminating conditions: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180°) and measured the adhesive force.

In one embodiment, the gas generating layer has specific adhesion. The adhesive force of the gas generating layer of the adhesive sheet of the present invention relative to SUS430 is preferably 0.1 N/20 mm or more, more preferably 0.5 N/20 mm to 50 N/20 mm, and further preferably 1 N/20 mm. ~40 N/20 mm, preferably 1.5 N/20 mm ~ 30 N/20 mm, and optimally 2 N/20 mm ~ 20 N/20 mm. If it is within this range, it is possible to obtain an adhesive sheet that exhibits good adhesiveness as a temporary fixing sheet used in the manufacture of electronic components, for example.

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 further preferably 5 μm to 120 μm.

The haze value of the adhesive sheet of the present invention is preferably 50% or less, more preferably 0.1% to 40%, and further preferably 0.5% to 30%. If it is within this range, the adherend (for example, a stand for temporarily fixing electronic components) can be seen through the adhesive sheet, and a mark placed on the fixing stand to indicate the temporary fixing position of the electronic component can be obtained. An adhesive sheet with excellent visibility. The adhesive sheet of the present invention can be configured so that each layer of the adhesive sheet does not contain insoluble fillers. Therefore, it can be an adhesive sheet with a low haze value and excellent visibility of the adherend as described above. This effect is an excellent effect that cannot be obtained by using an adhesive sheet containing insoluble fillers (for example, thermally expandable microspheres).

The water vapor transmittance 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, and still more preferably 4500 g/(m ² ·day). day) or less, and more preferably 4200 g/(m ² ·day) or less. In an adhesive sheet with a water vapor transmittance in this range, the gas generated by laser light irradiation is prevented from escaping, and a deformation portion with an excellent shape is formed in the adhesive layer. If such an adhesive sheet is used, small adherends (for example, electronic components) can be peeled off with high precision. The lower the water vapor transmission rate of the adhesive sheet of the present invention, the better, and its lower limit is, for example, 0.1 g/(m ² ·day). The water vapor transmission rate can be measured in an environment of 30°C and 90% RH by the measurement method according to JIS K7129B.

The water vapor transmission rate of the laminate including the adhesive layer and the intermediate layer is preferably 10,000 g/(m ² · day) or less, more preferably 7,000 g/(m ² · day) or less, and still more preferably 5,000 g /(m ²・day) or less, more preferably 4800 g/(m ²・day) or less, further preferably 4500 g/(m ²・day) or less, especially 4200 g/(m ²・day) )the following. If it is within this range, the laminate including the adhesive layer and the intermediate layer will function well as a gas barrier layer, and a deformation portion with an excellent shape will be formed in the adhesive layer. If such an adhesive sheet is used, small adherends (for example, electronic components) can be peeled off with high precision. The lower the water vapor transmission rate of the laminate including the adhesive layer and the intermediate layer, the better. The lower limit is, for example, 1 g/(m ² ·day).

The puncture strength of the laminate including the 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. If it is within this range, the laminate including the adhesive layer and the intermediate layer functions well as a gas barrier layer and preferably produces a shape change caused by the generation of gas. As a result, the adhesive layer is formed Excellent shape deformation part. If such an adhesive sheet is used, small adherends (for example, electronic components) can be peeled off with high precision. As shown in Figure 3, the puncture strength is measured by using a compression tester 6 (manufactured by Kato Tech, trade name "KES-G5"), and clamping the sample 4 (for example, a laminated body) with a circular opening having a diameter of 11.28 mm. Sample holders 5A and 5B are used for measurement. More specifically, at a measurement temperature of 23°C, a puncture needle (radius of curvature: 1 mm) can be pierced into the sample (piercing speed: 0.1 mm/s) at the center of the circular opening. The maximum load at the rupture point is taken as the puncture strength.

The ultraviolet transmittance at a wavelength of 360 nm of the laminate including the 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 of the adhesive sheet at a wavelength of 360 nm is, for example, 0% (preferably 0.05%, more preferably 0.1%).

The 10% weight reduction temperature of the adhesive sheet is preferably 200°C to 500°C, more preferably 220°C to 450°C, further preferably 250°C to 400°C, and particularly preferably 270°C to 370°C. If it is within this range, an adhesive sheet that can form a more favorable deformation portion by laser light irradiation can be obtained. The so-called 10% weight reduction temperature of the adhesive sheet refers to a 10% weight loss relative to the weight before heating (that is, the weight of the adhesive sheet becomes 90% relative to the weight before irradiation) in TGA analysis when the adhesive sheet is heated. %) temperature at the time point.

B. Gas Generating Layer The gas generating layer may 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 absorbs laser light and vaporizes 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 produce a deformed portion (for example, a concave and convex portion) at any part of the adhesive layer, and the shape of the deformed portion (for example, a concave and convex portion) can be obtained The deviation is less. If such an adhesive sheet is used, a deformed portion (for example, a concave and convex portion) can be accurately produced at a desired location, and the effect of the present invention becomes remarkable. In addition, in this specification, the state of "being dissolved in the adhesive" means that the ultraviolet absorber does not exist in the form of particles in the gas generating layer. More specifically, the gas generating layer preferably does not contain an ultraviolet absorber having a particle size of 10 μm or more as measured by particle distribution in a cross section of the gas generating layer using X-ray CT (computer tomography). Furthermore, the gas generating layer may or may not contain insoluble components in the adhesive. In one embodiment, the presence and content of insoluble components in the gas generating layer are evaluated by the haze value of the gas generating layer. The smaller the haze value is, the smaller the content of insoluble components in the gas generating layer is evaluated. Preferably, the gas generating layer contains substantially no insoluble components in the adhesive.

The elastic modulus of the cross section of the gas generation layer obtained by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. If it is within this range, it is preferable to produce a shape change of the gas generation layer due to the generation of gas, and as a result, a deformation portion with 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 and penetration depth of the indenter when the indenter is pressed into the sample (for example, the adhesive surface) when loading and unloading. And the elastic modulus is calculated based on the obtained load-pressure depth curve. The elastic modulus obtained by the nanoindentation method is obtained as follows: For the displacement obtained by pressing a diamond Berkovich type (triangular pyramid type) probe vertically against a section cut out of the measurement target layer - The load hysteresis curve is numerically processed using the software (triboscan) provided with the measuring device. In this specification, the so-called elastic modulus of the cross-section obtained by the nanoindentation method is measured by using a nanoindentation instrument (Triboindenter TI-950 manufactured by Hysitron Inc) by a single indentation at a specific temperature (25°C). Method, the elastic modulus is measured under the measurement conditions of an intrusion speed of about 500 nm/sec, a withdrawal speed of about 500 nm/sec, and an indentation depth of about 1500 nm. Furthermore, the elastic modulus of the gas generating layer can be adjusted by the type of material contained in the layer, the structure of the base polymer constituting the material, the type and amount of additives added to the layer, and the like. Furthermore, in this specification, when the cross section or the surface is not mentioned and only the elastic modulus obtained by the nanoindentation method is mentioned, the elastic modulus refers to the elastic modulus of the cross section obtained by the nanoindentation method.

The elastic modulus of the surface of the gas generation layer obtained by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. If it is within this range, it is preferable to produce a shape change of the gas generation layer due to the generation of gas, and as a result, a deformation portion with 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 and penetration depth of the indenter when the indenter is pressed into the sample (for example, the adhesive surface) when loading and unloading. And the elastic modulus is calculated based on the obtained load-pressure depth curve. The elastic modulus obtained by the nanoindentation method is obtained as follows: Regarding the displacement-load hysteresis curve obtained by pressing a diamond Berkovich type (triangular pyramid type) probe vertically against the measurement target layer, Numerical processing was performed using the software (triboscan) provided with the measuring device. In this specification, the so-called elastic modulus of the surface obtained by the nanoindentation method is measured by using a nanoindentation instrument (Triboindenter TI-950 manufactured by Hysitron Inc.) by a single indentation at a specific temperature (25°C). Method, the elastic modulus is measured under the measurement conditions of an intrusion speed of about 500 nm/sec, a withdrawal speed of about 500 nm/sec, and an indentation depth of about 3000 nm. Furthermore, the elastic modulus of the gas generating layer can be adjusted by the type of material contained in the layer, the structure of the base polymer constituting the material, the type and amount of additives added to the layer, and the like. In the present invention, the elastic modulus obtained by the nanoindentation method is measured by the above method using the cross section as the measurement surface, and the elastic modulus obtained by the nanoindentation method is measured by the above method using the surface as the measurement surface. There is no significant difference in modulus. When it is difficult to measure from the cross section, the value measured from the surface can be used as the measured value from the cross section.

The gasification starting 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, and particularly preferably 200°C to 400°C. If it is within this range, an adhesive sheet that can form a more favorable deformation portion by laser light irradiation can be obtained. In addition, in this specification, the gasification start temperature of the gas generation layer refers to the gas generation rising temperature calculated based on EGA analysis (evolved gas analysis) when the adhesive sheet is heated. The so-called rising gas generation temperature is defined as the temperature that reaches half the maximum gas generation peak value of the EGA/MS spectrum obtained by EGA analysis. The lower the gasification starting temperature is, the lower the temperature at which gas begins to be generated when laser light is irradiated. A sufficient amount of gas will also be generated when lower power is used for laser light irradiation. In one embodiment, the gasification starting temperature of the gas generating layer is equivalent to the gasification starting temperature of the ultraviolet absorber.

The 10% weight loss temperature of the gas generating layer is preferably 150°C to 500°C, more preferably 170°C to 450°C, and further preferably 200°C to 400°C. If it is within this range, an adhesive sheet that can form a more favorable deformation portion by laser light irradiation can be obtained. The so-called 10% weight loss temperature of the gas generating layer refers to the weight of the gas generating layer relative to the temperature rise in TGA analysis (thermogravimetric analysis, thermogravimetric analysis) when the adhesive sheet is heated (for example, when the temperature is raised by irradiation with laser light). The temperature at the time point when the weight of the gas generation layer is reduced by 10% by weight (that is, the weight of the gas generation layer becomes 90% of the weight before temperature rise).

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. If it is within this range, an adhesive sheet that can form a more favorable deformation portion by laser light irradiation can be obtained.

The elastic modulus Er(gas) [unit: MPa] and thickness h(gas) [unit: μm] of the gas generation 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 to satisfy the above formula (1), it is possible to prevent gas generation Excessive deformation caused by the gas generated in the generating layer allows the adhesive sheet to be deformed well by laser light irradiation. By forming this kind of gas generating layer, surface deformation can occur within a small range without arranging a thick barrier layer (adhesive layer) as a layer to prevent excessive deformation, and the adhesive layer (gas barrier layer) can be formed softly. ).

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) If it is in this 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 gas generating layer 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 of the gas generating layer at a wavelength of 360 nm 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 further preferably 0.5% to 40%.

B-1.UV absorber As the ultraviolet absorber, any appropriate ultraviolet absorber can be used as long as the effects of the present invention are obtained. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, trisulfide-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. Absorbents, etc. Among them, a trifluoroethylene ultraviolet absorber or a benzotriazole ultraviolet absorber is preferred, and a trizotriazole ultraviolet absorber is particularly preferred. Especially when an acrylic adhesive is used as the adhesive A, the trifluoroethylene ultraviolet absorber has a high compatibility with the base polymer of the acrylic adhesive, so it can be preferably used. The trifluoroethylene-based ultraviolet absorber preferably contains a compound having a hydroxyl group, and particularly preferably is an ultraviolet absorber containing a hydroxyphenyl trifluoroethylene-based compound (hydroxyphenyl trifluoroethylene-based ultraviolet absorber).

Examples of the hydroxyphenyltrixamethonium-based ultraviolet absorbers include: 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-trixamethonium-2-yl)- Reaction product of 5-hydroxybenzene and [(C10-C16 (mainly C12-C13) alkoxy) methyl] ethylene oxide (trade name "TINUVIN 400", manufactured by BASF), 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-trihydroxyphenyl and glycidic acid (2-ethylhexyl) Reaction product of ester (trade name "TINUVIN 405", manufactured by BASF), 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl) -1,3,5-Trisulfin (trade name "TINUVIN 460", manufactured by BASF), 2-(4,6-diphenyl-1,3,5-trissac-2-yl)-5-[ (Hexyl)oxy]phenol (trade name "TINUVIN 1577", manufactured by BASF), 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-tribenzoyl (trade name "TINUVIN 479", manufactured by BASF), trade name "TINUVIN 477" manufactured by BASF "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), phenylpropionic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and linear alkyl) ester compound (trade name "TINUVIN 384-2", manufactured by BASF), 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzo Triazol-2-yl)phenyl]octyl propionate and 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propanate A mixture of 2-ethylhexyl acid (trade name "TINUVIN 109", manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1- Phenylethyl)phenol (trade name "TINUVIN 900", manufactured by BASF), 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- Reaction product of tert-butyl-4-hydroxyphenyl)methyl propionate/polyethylene glycol 300 (trade name "TINUVIN 1130", manufactured by BASF), 2-(2H-benzotriazol-2-yl) ) p-cresol (trade name "TINUVIN P", manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol (trade name "TINUVIN 234", manufactured by BASF), 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-tertiary amylphenol (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), 2,2'- Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (trade name "TINUVIN 360", manufactured by BASF ), 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", manufactured by BASF Corporation), 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", Shipro Kasei company), 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalyliminomethyl)phenol ( Trade name "SEESORB 706", manufactured by Shipro Kasei Co., Ltd.), 2-(4-benzyloxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole (trade name, manufactured by Shipro Kasei Co., Ltd. SEESORB 7012BA"), 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (trade name "KEMISORB 73", manufactured by Chemipro Kasei Co., Ltd.), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tertiary octylphenol] (trade name "Adekastab LA-31", manufactured by ADEKA Co., Ltd.), 2-(2H-benzotriazole-2-yl)-p-cresol (trade name "Adekastab LA-32", manufactured by ADEKA Co., Ltd.), 2-(5-chloro-2H-benzotriazole-2- methyl)-6-tert-butyl-4-methylphenol (trade name "Adekastab LA-36", manufactured by ADEKA Co., Ltd.), etc.

The molecular weight of the compound constituting the ultraviolet absorber is preferably 200 to 1,500, more preferably 250 to 1,200, further preferably 300 to 1,000. If it is within this range, an adhesive sheet that can form a more favorable deformation 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 further 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. If it is within this range, an adhesive sheet that can form a more favorable deformation portion by laser light irradiation can be obtained.

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

Examples of the acrylic adhesive include an acrylic polymer (homopolymer or copolymer) using one or more alkyl (meth)acrylates as monomer components as a base polymer. Acrylic adhesive, etc. Specific examples of (meth)acrylic acid alkyl esters include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid isopropyl ester, Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third 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 Isononyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate Tridecyl acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate , C1-20 alkyl (meth)acrylate such as octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosanyl (meth)acrylate. Among them, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having a carbon number of 4 to 18 are preferably used.

The above-mentioned acrylic polymer may also contain units corresponding to other monomer components copolymerizable with the above-mentioned alkyl (meth)acrylate for the purpose of modifying cohesive force, heat resistance, cross-linkability, etc., if necessary. Examples of such monomer components include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like containing carboxyl groups. Monomers; anhydride monomers such as maleic anhydride and Iconic anhydride; (meth)hydroxyethyl acrylate, (meth)hydroxypropyl acrylate, (meth)hydroxybutyl acrylate, (meth)acrylic acid Hydroxyl hexyl ester, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate and other hydroxyl-containing monomers Body; Styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, (meth)acrylic acid sulfopropyl ester , (meth)acryloxynaphthalene sulfonic acid and other sulfonic acid group-containing monomers; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide (N-substituted) amide monomers such as N-hydroxymethyl (meth)acrylamide, N-hydroxymethylpropane (meth)acrylamide, etc.; (meth)acrylic acid amine (meth)acrylic acid aminoalkyl ester monomers such as ethyl ester, N,N-dimethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, etc.; (meth)acrylic acid alkoxyalkyl ester monomers such as methoxyethyl methacrylate and ethoxyethyl (meth)acrylate; N-cyclohexylmaleimide, N- Isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and other maleimide monomers; N-methyl Ikonimide, N-Ethyl Iconimide, N-Butyl Iconimide, N-Octyl Iconimide, N-2-Ethylhexyl Iconimide, N -Iconidimine-based monomers such as cyclohexyl itonimide and N-lauryl itonimide; N-(meth)acryloxymethylenesuccinimide, N-( Meth)acryl-6-oxyhexamethylene succinimide, N-(meth)acryl-8-oxyoctamethylene succinimide and other succinimines Monomers; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperdine, vinyl Ethylene such as pyridine, vinylpyrrole, vinylimidazole, vinylethazole, vinylpyridine, N-vinylcarboxamides, styrene, α-methylstyrene, N-vinylcaprolactamide, etc. Base monomers; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy-containing acrylic monomers such as glycidyl (meth)acrylate; (meth)acrylic polyethylene glycol, (meth)acrylic acid polyethylene glycol, Diol acrylate monomers such as meth)acrylic acid polypropylene glycol, (meth)acrylic acid methoxyethylene glycol, (meth)acrylic acid methoxypolypropylene glycol, etc.; (meth)acrylic acid tetrahydrofuran methyl ester, fluorine (meth)acrylate Acrylate monomers with heterocyclic rings, halogen atoms, silicon atoms, etc.; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, etc. Meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Ester, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, acrylic polyester, acrylic urethane and other multi-functional monomers; isoprene, butadiene , isobutylene and other olefin monomers; vinyl ether and other vinyl ether monomers, etc. These monomer components can be used individually or in combination of 2 or more types.

Examples of the rubber-based adhesive include rubber-based adhesives using 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 Ethylene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, recycled rubber, butadiene base rubber, polyisobutylene, their modified bodies and other synthetic rubbers.

The gas generated from the gas generating layer is preferably a hydrocarbon (preferably aliphatic hydrocarbon) gas. The gas generating layer capable of generating hydrocarbon-based gas is composed of a hydrocarbon-based compound as its main component, for example. The gas generating layer preferably does not contain compounds containing halogen elements. If the generated gas is a hydrocarbon-based gas, corrosion of electronic parts as the workpiece can be prevented. This effect becomes more remarkable 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 The optimal range is 13 m/z～400 m/z.

The above-mentioned adhesive A may contain any appropriate additives if necessary. Examples of the additive include cross-linking agents, tackifiers (eg, rosin-based tackifiers, terpene-based tackifiers, hydrocarbon-based tackifiers, etc.), plasticizers (eg, trimellitic acid). Ester plasticizer, pyromellitate plasticizer), pigments, dyes, anti-aging agents, conductive materials, antistatic agents, light stabilizers, peeling adjusters, softeners, surfactants, flame retardants agents, antioxidants, etc.

Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, and metal alkoxide-based cross-linking agents. 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 Agents, etc. Among them, an isocyanate cross-linking agent or an epoxy cross-linking agent is preferred.

Specific examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophoride Alicyclic isocyanates such as ketone 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 "Coronate L") Coronate HL"), isocyanate adducts such as the isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "Coronate HX"), etc. The content of the isocyanate cross-linking agent can be set to any appropriate amount according to the required adhesion. It is typically 0.1 to 20 parts by weight relative to 100 parts by weight of the base polymer, and more preferably 0.5 parts by weight. ~10 parts by weight.

Examples of the epoxy cross-linking agent include: N,N,N',N'-tetraglycidyl metaxylylenediamine, diglycidyl aniline, 1,3-bis(N,N- Glycidyl aminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C"), 1,6-hexanediol diglycidyl ether (manufactured by Kyoeisha 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 Nippon Oils and Fats Co., Ltd., trade name "EPIOL E-400"), polypropylene glycol diglycidyl ether Ether (manufactured by Nippon Oils and Fats Corporation, trade name "EPIOL P-200"), sorbitol polyglycidyl ether (manufactured by Nagase chemteX Company, trade name "Denacol EX-611"), glycerol polyglycidyl ether (manufactured by Nagase chemteX Company, Trade name "Denacol EX-314"), pentaerythritol polyglycidyl ether, polyglyceryl polyglycidyl ether (manufactured by Nagase chemteX, trade name "Denacol EX-512"), sorbitan polyglycidyl ether, trimethylol Propane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, tris(2-hydroxyethyl)triglycidyl isocyanurate, resorcinol diglycidyl ether, bisphenol -S-diglycidyl ether, epoxy resins with two or more epoxy groups in the molecule, etc. The content of the epoxy cross-linking agent can be set to any appropriate amount according to the required adhesion. It is typically 0.01 to 10 parts by weight relative to 100 parts by weight of the base polymer, and more preferably 0.03 parts by weight. parts to 5 parts by weight.

C. Adhesive layer The above adhesive layer contains any appropriate adhesive B. The adhesive B may be a pressure-sensitive adhesive B1 or a hardening adhesive B2.

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, and particularly preferably 2 μm to 20 μm. If it is within this range, an adhesive layer can be formed that has good adhesion and functions well as a gas barrier layer.

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 further preferably 7000 g/(m ² ·day) or less, more preferably 5000 g/(m ² ·day) or less, still more preferably 4800 g/(m ² ·day) or less, particularly preferably 4500 g/(m ² ·day) or less. If it is within this range, the adhesive layer will function well as a gas barrier layer and form a deformation portion with an excellent shape. If such an adhesive sheet is used, small adherends (for example, electronic components) can be peeled off with high precision. The lower the water vapor transmission rate of the adhesive layer, the better. 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. If it is within this range, the adhesive layer will function well as a gas barrier layer and will preferably produce a shape change caused by the generation of gas. As a result, a deformation portion with an excellent shape will be formed. If such an adhesive sheet is used, small adherends (for example, electronic components) 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%, and more preferably 60% to 95%.

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

C-2. Hardening adhesive B2 Examples of the curing adhesive B2 include thermosetting adhesives, active energy ray curing adhesives, and the like. It is preferable to use an active energy ray-hardening adhesive. The above-mentioned adhesive layer formed by the active energy ray curable adhesive is an adhesive layer formed by irradiation of active energy rays, that is, an adhesive layer with specific adhesive force after irradiation of active energy rays.

Examples of the resin material constituting the above-mentioned active energy ray curable adhesive include ultraviolet curing system (authored by Kiyoshi Kato, published by the Comprehensive Technology Center (1989)), photocuring technology (edited by the Technical Information Association (2000)), Resin materials described in Japanese Patent Application Laid-Open No. 2003-292916, Japanese Patent No. 4151850, etc. More specifically, examples thereof include a resin material (B2-1) containing a polymer serving as a mother agent and an active energy ray-reactive compound (monomer or oligomer), and a resin material containing an active energy ray-reactive polymer. (B2-2) etc.

Examples of the polymer used as the masterbatch include natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, recycled rubber, and butyl rubber. Rubber-based polymers such as rubber, polyisobutylene rubber, and nitrile rubber (NBR (Nitrile Butadiene Rubber)); silicone-based polymers; acrylic-based polymers, etc. These polymers can be used individually or in combination of 2 or more types.

Examples of the active energy ray reactive compounds include photoreactive compounds containing a plurality of functional groups having carbon-carbon multiple bonds such as acrylic groups, methacrylic groups, vinyl groups, allyl groups, 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 free radicals by ultraviolet rays. Therefore, if this compound is used, an adhesive layer that can be cured in a short time can be formed. Furthermore, if a (meth)acrylic compound having an ethylenically unsaturated functional group is used, an adhesive layer having moderate hardness after curing can be formed. Specific examples of the photoreactive monomer or oligomer include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. ) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, Compounds containing (meth)acrylyl groups such as 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and (meth)acrylic urethane compounds ; Dimers to pentamers of the (meth)acrylyl group-containing compound, etc. These compounds can be used individually or in combination of 2 or more types.

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

Furthermore, as the active energy ray reactive compound, a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocyclic rings in the molecule can be used. When the mixture is irradiated with active energy rays (eg, ultraviolet rays, electron beams), the organic salt will be decomposed to generate ions, which become starting species and trigger a ring-opening reaction of the heterocycle, thereby forming a three-dimensional network structure. Examples of the organic salts include iodonium salts, phosphonium salts, antimony salts, sulfonium salts, and borate salts. Examples of the heterocyclic ring in the compound having a plurality of heterocyclic rings in the molecule include ethylene oxide, oxetane, oxolane, ethylene sulfide, and aziridine.

In the resin material (B2-1) containing the above-described polymer as a masterbatch and an active energy ray-reactive compound, the content ratio of the active energy ray-reactive compound is preferably 0.1 relative to 100 parts by weight of the polymer as a masterbatch. Parts by weight to 500 parts by weight, more preferably 1 part by weight to 300 parts by weight, further preferably 10 parts by weight to 200 parts by weight.

Examples of the active energy ray reactive polymer include those containing active energy ray reactive functional groups having carbon-carbon multiple bonds such as acrylic group, methacrylic group, vinyl group, allyl group, and ethynyl group. polymer. It is preferable to use a compound (polymer) having an ethylenically unsaturated functional group, and more preferably to use a (meth)acrylic polymer having an acrylic group or a methacrylic group. Specific examples of the polymer having an active energy ray-reactive functional group include a polymer containing polyfunctional (meth)acrylate. The polymer containing polyfunctional (meth)acrylate is preferably an alkyl ester having a carbon number of 4 or more in the side chain, more preferably an alkyl ester having a carbon number of 6 or more, and still more preferably a carbon The alkyl ester having a carbon number of 8 or more is particularly preferably an alkyl ester having a carbon number of 8 to 20, and most preferably an alkyl ester having a carbon number of 8 to 18.

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 above-mentioned active energy ray curable adhesive can be hardened by irradiation of active energy rays. In the adhesive sheet of the present invention, after the adherend is attached before hardening the adhesive, active energy rays are irradiated to harden the adhesive, whereby the adherend can be brought into close contact with the adherend. Examples of the active energy rays include γ rays, ultraviolet rays, visible rays, infrared rays (heat lines), radio frequency waves, α rays, β rays, electron beams, plasma currents, ionizing radiation, particle beams, and the like. Conditions such as the wavelength and irradiation dose of active energy rays can be set to any appropriate conditions depending on the type of resin material used. For example, the adhesive can be hardened by irradiating ultraviolet light with a dose of 10 to 1000 mJ/cm ² .

D. Intermediate Layer Examples of the form of the above-mentioned intermediate layer include a resin layer, an adhesive layer, and the like.

In one embodiment, the intermediate layer contains 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 other embodiments, the intermediate layer contains curable resin (for example, ultraviolet curable resin, thermosetting resin). This 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 further preferably 1.5 μm to 30 μm. If it is within this 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, further preferably 4500 g/(m ² ·day) or less , and more preferably 4200 g/(m ² ·day) or less. If it is within this range, the intermediate layer will function well as a gas barrier layer and form a deformation portion with an excellent shape. If such an adhesive sheet is used, small adherends (for example, electronic components) can be peeled off with high precision. The lower the water vapor transmission rate of the intermediate layer, the better. 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 further preferably 1000 mN to 4000 mN. If it is within this range, the intermediate layer functions well as a gas barrier layer and preferably causes a shape change caused by the generation of gas. As a result, a deformed portion with an excellent shape is formed. If such an adhesive sheet is used, small adherends (for example, electronic components) 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%, and more preferably 60% to 95%.

D-1. As an intermediate layer between 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 resin, polyolefin resin, styrene elastomer resin (such as SEBS, etc.), ultraviolet curable resin, thermosetting resin, amine Formate-based resins, epoxy-based resins, etc. In one embodiment, the resin film includes thermoplastic resin.

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

D-2. As the middle of the adhesive layer Examples of the intermediate layer that is an adhesive layer include an intermediate layer containing a pressure-sensitive adhesive, an intermediate layer containing a hardening adhesive, and the like. It is preferable to configure an intermediate layer containing hardening adhesive D. In particular, if an adhesive layer containing a pressure-sensitive adhesive A and an intermediate layer containing a hardening adhesive D are combined as an adhesive layer, an adhesive sheet can be obtained that can form a better deformation portion by laser irradiation. . As the hardening adhesive D, the adhesive described in 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. An example of the adhesive sheet of the present invention is as follows: a gas generating layer forming composition containing an adhesive A and an ultraviolet absorber is directly coated on a specific substrate to form a gas generating layer, and the gas generating layer is formed on a specific substrate. An adhesive layer-forming composition containing 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 intermediate layer-forming composition is applied to the gas generating layer to form the intermediate layer, and the intermediate layer is coated with The cloth adhesive layer forming composition is used to form an adhesive layer. Alternatively, each layer may be formed separately and then laminated together to form an adhesive sheet.

As the coating method of the above composition, any appropriate coating method can be used. For example, each layer can be formed by drying after coating. Examples of the coating method include a coating method using a multi-roller coater, a die coater, a gravure coater, an applicator, and the like. Examples of drying methods include natural drying, heat drying, and the like. The heating temperature when performing heat drying can be set to any appropriate temperature according to the characteristics 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 components The processing method of electronic components of the present invention includes: attaching electronic components to the above-mentioned adhesive sheet; and irradiating the adhesive sheet with laser light to peel off the electronic components from the adhesive sheet. Examples of electronic components include semiconductor wafers, LED (Light-emitting diode) wafers, MLCC (Multi-layer Ceramic Capacitors), and the like.

The above-mentioned peeling off of the electronic components can be performed at selected locations. Specifically, by attaching and fixing multiple electronic components to an adhesive sheet, the electronic components can be peeled off in such a way that part of the electronic components can be peeled off while other electronic components remain fixed.

In one embodiment, the processing method of electronic components of the present invention includes: performing specific processing on the electronic components after attaching the electronic components to the adhesive sheet and before peeling off the electronic components from the adhesive sheet. The above-mentioned processing is not particularly limited, and examples include: grinding processing, cutting processing, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer, alignment, repair, and installation. Surface protection and other treatments.

The size of the above-mentioned electronic component (the area of the attachment surface) is, for example, 1 μm ² to 250000 μm ² . In one embodiment, electronic components whose size (the area of the attachment surface) ranges from 1 μm ² to 6400 μm ² can be supplied to the process. In other embodiments, electronic components with a size (area of the attachment surface) ranging from 1 μm ² to 2500 μm ² may be provided for processing.

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

As the laser light, for example, UV laser light can be used. The irradiation power of 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 above-mentioned processing method of electronic components includes: after peeling off the electronic components, arranging the electronic components on other sheets (eg, adhesive sheets, substrates, 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 off the separator was used. In addition, in the examples, unless otherwise clearly stated, "parts" and "%" are based on weight.

(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-Visible Spectrophotometer SolidSpec 3700", manufactured by Shimadzu Corporation) to let the incident light Vertically incident on the gas barrier layer side of the sample, and measure the transmittance in the wavelength range of 300 nm to 800 nm. The transmittance at the wavelength of 360 nm of the selected transmission spectrum. In the case of an adhesive sheet consisting only of an adhesive layer, the measurement is performed by placing the release liner on one side in a spectrophotometer, and then measuring the transmission spectrum of the release liner alone. Subtraction operation is performed to obtain the transmission spectrum of the adhesive layer alone. The transmittance at the wavelength of 360 nm of the selected transmission spectrum. (2) Maximum peak gas generation temperature. Approximately 0.5 mg of the adhesive sheet sample was placed in a furnace-type pyrolyzer, and a mass chromatogram was obtained by performing mass analysis of the components volatilized by heating using EGA-MS. A heating furnace type pyrolyzer (manufactured by Frontier Laboratories, trade name "PY2020iD") was used to increase the temperature from 40°C to 500°C at a temperature rise rate of 10°C/min, and GC/MS (Gas chromatography/mass spectrometry, gas chromatography mass spectrometry) was used. ) analysis device (manufactured by JEOL Corporation, trade name "JMS-T100GCV"), calculates the maximum gas generation peak temperature based on the mass chromatogram in the mass range m/z=10 to 800. (3) Vaporization start temperature: The adhesive sheet is heated in the same manner as in (2) above, and the rising temperature of gas generation calculated based on EGA analysis is used as the vaporization start temperature. The gas production rising temperature is defined as the temperature that reaches half the maximum gas production peak value of the EGA/MS chromatogram obtained by EGA analysis. (4) Generated gas species: The adhesive sheet sample was placed in an automatic sample combustion device (manufactured by Mitsubishi Chemical Analytical Technology Co., Ltd., trade name "AQF-2100H"), and the gas generated by heating at 400°C for 30 minutes was captured. By analyzing the capture liquid using ion chromatography, the gas species produced are identified. (5) Use a differential thermal analysis device (manufactured by TA Instruments, trade name "Discovery TGA") at the 5% weight loss temperature, set the flow rate to 25 ml/min under a heating temperature of 10°C/min and an _N2 atmosphere. Determine the temperature at which the weight of the adhesive sheet decreases by 5%. (6) At the 10% weight loss temperature, use a differential thermal analysis device (manufactured by TA Instruments, trade name "Discovery TGA"), set the flow rate to 25 ml/min under a heating temperature of 10°C/min and an _N2 atmosphere. Determine the temperature at which the weight of the adhesive sheet decreases by 10%. The 10% weight loss temperature was measured for each of the adhesive sheet and gas generating layer (UV absorber). (7) Water Vapor Transmission Rate A measurement sample was prepared by attaching a sample so as to cover the opening of an Al jig having an opening of 10 mm × 10 mm, and set the measurement sample in a water vapor transmission measuring device (MOCON (manufactured by the company, trade name "PERMATRAN-W3/34G") between the first chamber and the second chamber, the MOCON measurement method was used to evaluate. The temperature and humidity conditions are set to 30°C/90% RH, the gas (water vapor) flow rate is set to 10.0±0.5 cc/min, and the measurement time is set to 20 hours. The water vapor transmission rate was measured separately for the adhesive sheet, adhesive layer, and intermediate layer. (8) The surface shape changes when the gas generating layer side of the adhesive sheet (the side opposite to the adhesive layer) is bonded to a glass plate (manufactured by Matsunami Glass Co., Ltd., large glass slide S9112 (standard large white edge No. 2)) and obtain the measurement sample. From the glass plate side of the sample, use a wavelength of 355 nm and a beam diameter of about 20 μm. The UV laser light is used for pulse scanning with a power of 0.80 mW and a frequency of 40 kHz to generate gas from the gas generation layer. For the surface of the adhesive layer corresponding to any point scanned by the pulse, observe it using a confocal focusing laser microscope 1 minute after the laser irradiation ends, and measure the vertical displacement Y and horizontal displacement X (diameter; full width at half maximum) value). When the displacement Y is 8 μm or more, the peelability is significantly excellent (in the table, ◎); when the displacement Y is 0.6 μm or more and less than 8 μm, the peelability is good (in the table, ○); when the displacement When Y is less than 0.6 μm, the releasability is insufficient (× in the table). (9) Adhesion (gas generating layer side) PET#25 was bonded to the adhesive layer side of the adhesive sheet to obtain a measurement sample. The adhesion of the gas generating layer side of the sample to SUS430 was measured according to the method of JIS Z 0237:2000 (Laminating conditions: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180° ) is measured. (10) Adhesion (adhesive layer) PET#25 was bonded to the gas generating layer side of the adhesive sheet to obtain a measurement sample. The adhesion of the adhesive layer side of the sample to SUS430 was measured according to the method of JIS Z 0237:2000 (laminated conditions: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180° ) is measured. (11) In-plane uniformity of deformation The gas generation layer is irradiated with UV laser light in the manner described in (8) above. Use a microscope to observe the deformed parts in a randomly selected 2 mm × 2 mm range. When more than 90% of the convex parts are of the same size, it is regarded as good (in the table, 0). When more than 80% of the convex parts are of the same size, it is regarded as good (0). If less than 90% of the convex parts are of the same size, it is set as acceptable (in the table, △), and when less than 80% of the convex parts are of the same size, it is set as poor (in the table, ×). The so-called same size means that the difference in displacement X is within ±20%. (12) Position selectivity of deformation The gas generation layer is irradiated with UV laser light in the manner of (8) above. The case where only the laser irradiated part is deformed alone is rated as pass (0), and the case where there are also multiple deformations around the laser irradiated part is rated as failed (×). (13) Elastic modulus using a nanoindentation instrument (Triboindenter TI-950 manufactured by Hysitron Inc), through a single indentation method at a specific temperature (25°C), at an indentation speed of about 500 nm/sec, and pulling out The elastic modulus of the cross-section of the gas generation layer is measured under the measurement conditions of an exit speed of approximately 500 nm/sec and an intrusion depth of approximately 1500 nm.

[Production Example 1] Preparation of adhesive a Add 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 to toluene. After adding 0.2 parts by weight of benzyl, the mixture was heated to 70° C. to obtain a toluene solution of an acrylic copolymer (polymer A). A toluene solution of polymer A (polymer A: 100 parts by weight), 3 parts by weight of isocyanate cross-linking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L"), and surfactant (manufactured by Kao Co., Ltd., trade name "EXCEPARL IPP") 5 parts by weight were mixed to prepare adhesive a. The composition of adhesive a is shown in Table 1.

[Production Example 2] Preparation of adhesive b After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, the acrylic copolymer ( Solution of polymer A2) in ethyl acetate. An ethyl acetate solution of polymer A2 (polymer A2: 100 parts by weight), 1 part by weight of an epoxy cross-linking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), and an isocyanate cross-linking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L") 3 parts by weight were mixed to prepare adhesive b. The composition of adhesive b is shown in Table 1.

[Production Example 3] Preparation of Adhesive I Adhesive I was prepared in the same manner as in Production Example 1 except that the compounding amount of the cross-linking agent was 1 part by weight and no surfactant was contained. The composition of adhesive I is shown in Table 1.

[Production Example 3'] Preparation of adhesive c The adhesive c was prepared in the same manner as in Production Example 2, except that the amount of the isocyanate cross-linking agent was 1 part by weight and the amount of the epoxy cross-linking agent was 0.4 parts by weight. The composition of adhesive c is shown in Table 1.

[Table 1] Adhesive composition Production Example 1 Adhesive a Production Example 2 Adhesive b Production Example 3 Adhesive I Production Example 3' Adhesive c base polymer Material Acrylic Acrylic Acrylic Acrylic Polymer species Polymer A Polymer C Polymer A Polymer C Cross-linking agent Cross-linking agent type Isocyanate series Isocyanate series Isocyanate series Isocyanate series Product name, number of copies Coronate/L(3) Coronate/L(3) Coronate/L(1) Coronate/L(l) Cross-linking agent type - Epoxy system - Epoxy system Product name, number of copies - Tetrad C(1) - Tetrad C(0.4) surfactant Surfactant species Fatty acid ester series - - - Product name, number of copies EXCEPARL IPP(5) - - - Examples 1 to 14 Comparative Examples 1 to 3 Examples 15 and 16 Comparative examples 4 to 5 Examples 17 and 18

[Production Example 4] Preparation of intermediate layer forming composition a 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 benzoyl peroxide as a polymerization initiator to ethyl acetate, heat to 70°C. An ethyl acetate solution of an acrylic copolymer (polymer B) was obtained. An ethyl acetate solution of polymer B (polymer B: 100 parts by weight), 1 part by weight of epoxy cross-linking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C"), UV oligomer (Mitsubishi Chemical Co., Ltd. The intermediate layer forming composition a was prepared by mixing 50 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "Omnirad 127") and 3 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "Omnirad 127"). Table 2 shows the composition of the intermediate layer forming composition a.

[Production Example 5] Preparation of intermediate layer forming composition b. Maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (SEBS: styrene part/ethylene-butylene part (weight Ratio) = 30/70, acid value: 10 (mg-CH ₃ ONa/g), manufactured by Asahi Kasei Chemical Company, trade name "Tuftec M1913") 100 parts by weight, epoxy cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, 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 toluene were mixed to obtain an intermediate layer forming composition b. The composition of the intermediate layer forming composition b is shown in Table 2.

[Table 2] Intermediate layer forming composition Production Example 4 Intermediate Layer Forming Composition a Production Example 5 Intermediate Layer Forming Composition b base polymer Material Acrylic SEBS Department Polymer species Polymer B UV oligomer UV oligomer UV hardening acrylic urethane - Product name, number of copies UV-1700B(50) - Cross-linking agent Cross-linking agent type Epoxy system Epoxy system Product name, number of copies Tetrad C(1) Tetrad C(3) Photopolymerization initiator Photopolymerization initiator Benzoanone series - Product name, number of copies Irg127(3) - Example 2 Example 3

[Production Example 6] Preparation of composition a for gas generation layer formation Polymer A was obtained in the same manner as in Production Example 1. A toluene solution of polymer A (polymer A: 100 parts by weight), 1.5 parts by weight of an isocyanate cross-linking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and an ultraviolet absorber (manufactured by BASF, trade name "Tinuvin 477") and 20 parts by weight were mixed to prepare a gas generating layer forming composition a. Table 3 shows the composition of the gas generating layer forming composition a.

[Production Example 7] Preparation of gas generation layer forming composition b The composition b for gas generation layer formation was prepared in the same manner as in Production Example 5 except that the compounding amount of the UV absorber was 10 parts by weight. Table 3 shows the composition of the gas generating layer forming composition b.

[Production Example 8] Preparation of composition c for gas generation layer formation As a UV absorber, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-trifluoroethylene (commercial product The composition c for forming a gas generating layer was prepared in the same manner as in Production Example 5, except that 10 parts by weight of "TINUVIN 460" (manufactured by BASF) was used. Table 3 shows the composition of the gas generating layer forming composition c.

[Manufacturing Example 9] Preparation of gas generating layer forming composition d As a UV absorber, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tri𠯤-2-yl)-5-hydroxybenzene and [(C10-C16 (Mainly C12-C13) alkoxy) methyl] ethylene oxide reaction product (trade name "TINUVIN 400", manufactured by BASF) was prepared in the same manner as in Production Example 5 except for 20 parts by weight. Composition d for forming a gas generating layer. Table 3 shows the composition of the gas generating layer forming composition d.

[Production Example 10] Preparation of gas generation layer forming composition e 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, the gas generating layer forming composition e was prepared in the same manner as in Production Example 5. Table 3 shows the composition of the gas generating layer forming composition e.

[Production Example 11] Preparation of composition f for forming gas generating layer Polymer B was obtained in the same manner as in Production Example 3. An ethyl acetate solution of polymer B (polymer B: 100 parts by weight), 1 part by weight of an isocyanate cross-linking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and a UV absorber (manufactured by BASF, Trade name "Tinuvin 477") 20 parts by weight were mixed to prepare a gas generating layer forming composition f. Table 3 shows the composition of the gas generating layer forming composition f.

[Production Example 12] Preparation of gas generation layer forming composition g After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, the acrylic copolymer ( Solution of 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 cross-linking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and an ultraviolet absorber (manufactured by BASF, Trade name "Tinuvin 477") 20 parts by weight were mixed to prepare a gas generating layer forming composition g. Table 3 shows the composition of the gas generating layer forming composition g.

[Production Example 13] Preparation of gas generation layer forming composition h After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, the acrylic copolymer ( Solution of polymer C) in ethyl acetate. An ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 0.1 part by weight of epoxy cross-linking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), and ultraviolet absorber (BASF Co., Ltd., trade name "Tinuvin 477") 20 parts by weight were mixed to prepare a gas generating layer forming composition h. Table 3 shows the composition of the gas generating layer forming composition h.

[Manufacturing Example 14] Preparation of the gas generating layer forming composition i. Maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (SEBS: styrene part/ethylene-butylene part ( 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 cross-linking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd. , trade name "TETRAD-C") 3 parts by weight, ultraviolet absorber (manufactured by BASF, trade name "Tinuvin 477") 20 parts by weight, and toluene as a solvent were mixed to prepare a gas generating layer forming composition i. Table 3 shows the composition of the gas generating layer forming composition i.

[Production Example 15] Preparation of gas generation layer forming composition I The composition I for forming a gas generation layer was prepared in the same manner as in Production Example 5 except that no ultraviolet absorber was blended. Table 3 shows the composition of the gas generating layer forming composition I.

[Production Example 16] Preparation of composition I containing thermally expandable microspheres The ultraviolet absorber was not blended, and the blending amount of the cross-linking agent was set to 1.4 parts by weight, and 30 parts by weight of heat-expandable microspheres (manufactured by Matsumoto Oils & Fats Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere F-50D") and terpene phenol series were blended. Composition I containing thermally expandable microspheres was prepared in the same manner as in Production Example 5, except that 10 parts by weight of tackifying resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name "SUMILITERESIN PR51732") was added.

[Production Example 17] Preparation of composition II containing thermally expandable microspheres Instead of 10 parts by weight of terpenol-based tackifier resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name "SUMILITERESIN PR51732"), 20 parts by weight of terpenol-based tackifier resin (manufactured by Yasuhara Chemical Co., Ltd., trade name "YS POLYSTER T160") was used , Except for this, a composition II containing thermally expandable microspheres was prepared in the same manner as in Production Example 13.

[Production Example 14'] Preparation of composition j for gas generation layer formation After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, the acrylic copolymer ( Solution of 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 cross-linking agent (trade name "Coronate L" manufactured by Nippon Polyurethane Co., Ltd.), and an epoxy-based cross-linking agent (Mitsubishi Gas A gas generating layer forming composition j was prepared by mixing 0.1 parts by weight of a UV absorber (manufactured by a chemical company, trade name "TETRAD-C") and 10 parts by weight of an ultraviolet absorber (manufactured by a BASF company, trade name "TINUVIN 400"). Table 3 shows the composition of the gas generating layer forming composition j.

[Manufacturing Example 14''] Preparation of gas generating layer forming composition k The composition k for gas generation layer formation was prepared in the same manner as in Production Example 14 except that the compounding amount of the UV absorber was 5 parts by weight. Table 3 shows the composition of the gas generating layer forming composition k.

[table 3] Composition for forming gas generating layer Production Example 6 Composition a for gas generation layer formation Production Example 7 Gas Generating Layer Forming Composition b Production Example 8 Composition c for gas generation layer formation Production Example 9 Composition d for gas generation layer formation Production Example 10 Gas Generating Layer Forming Composition e base polymer Material Acrylic Acrylic Acrylic Acrylic Acrylic Polymer species Polymer A Polymer A Polymer A Polymer A Polymer A Cross-linking agent Cross-linking agent type Isocyanate series Isocyanate series Isocyanate series Isocyanate series Isocyanate series Number of cross-linking agents Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) UV absorber UV absorber type (skeleton) Hydroxyphenyl triseries Hydroxyphenyl triseries Hydroxyphenyl triseries Hydroxyphenyl triseries Benzotriazole series Product name, number of copies Tinuvin477(20) Tinuvin477(10) Tinuvin460(10) Tinuvin400(20) Tinuvin326(20) Molecular weight of UV absorber 958.2 958.2 629.8 647.8 315.8 TGA10% weight reduction temperature [℃] 352.8 352.8 401.5 391.7 234.5 Maximum absorption wavelength of UV absorber 356nm 356nm 349 nm 336nm 355nm Remarks Examples 1 to 4, 9 to 12 Example 5 Example 6 Example 7 Example 8 Composition for forming gas generating layer Production Example 11 Composition f for gas generation layer formation Production Example 12 Composition g for forming a gas generating layer Production Example 13 Composition h for gas generation layer formation Production Example 14 Gas Generating Layer Forming Composition i Production Example 14' Composition j for gas generation layer formation Production Example 14'' Composition k for gas generation layer formation base polymer Material Acrylic Acrylic Acrylic SEBS Department Acrylic Acrylic Polymer species Polymer B Polymer C Polymer C Polymer C Polymer C Cross-linking agent Cross-linking agent type Isocyanate series Isocyanate series Epoxy system Epoxy system Isocyanate series Isocyanate series Number of cross-linking agents Coronate/L(1.0) Coronate/L(1.0) Tetrad C(0.1) Tetrad C(3) Coronate/L(1.0) Coronate/L(1.0) Cross-linking agent type Isocyanate series Isocyanate series Epoxy system Epoxy system Epoxy system Epoxy system Number of cross-linking agents Coronate/L(1.0) Coronate/L(1.0) Tetrad C(0.1) Tetrad C(3) Tetrad C(0.1) Tetrad C(0.1) UV absorber UV absorber type (skeleton) Hydroxyphenyl triseries Hydroxyphenyl triseries Hydroxyphenyl triseries Hydroxyphenyl triseries Hydroxyphenyl triseries Hydroxyphenyl triseries Product name, number of copies Tinuvin477(20) Tinuvin477(20) Tinuvin477(20) Tinuvin477(20) Tinuvin400(10) Tinuvin400(5) Molecular weight of UV absorber 958.2 958.2 958.2 958.2 647.8 647.8 TGA10% weight reduction temperature [℃] 352.8 352.8 352.8 352.8 391.7 391.7 Maximum absorption wavelength of UV absorber 356nm 356nm 356nm 356nm 336nm 336nm Remarks Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Composition for forming gas generating layer Production Example 15 Gas Generating Layer Forming Composition I Production Example 16 Composition I containing thermally expandable microspheres Production Example 17 Composition II containing thermally expandable microspheres base polymer Material Acrylic Acrylic Acrylic Polymer species Polymer A Polymer A Polymer A Cross-linking agent Cross-linking agent type Isocyanate series Isocyanate series Isocyanate series Number of cross-linking agents Coronate/L(1.5) Coronate/L(1.4) Coronate/L(1.4) UV absorber UV absorber type (skeleton) - - - Product name, number of copies - - - Molecular weight of UV absorber - - - TGA10% weight reduction temperature [℃] - - - Maximum absorption wavelength of UV absorber - - - Remarks Contains thermally expandable microspheres Contains thermally expandable microspheres Comparative example 1 Comparative example 2 Comparative example 3

[Example 1] The adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate film with a silicone release agent-treated surface (thickness: 75 μm), and then dried to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The gas generating layer forming composition a obtained in Production Example 6 was applied to polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after evaporation (drying) of the solvent became 7 μm. film (manufactured by Toray Corporation, trade name "Cerapeel", thickness: 38 μm), and then 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 generation layer precursor layer a are laminated between rollers to obtain a film sandwiched between polyethylene terephthalate films with silicone release agent-treated surfaces. Adhesive sheet (adhesive layer/gas generating layer). The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 2] The adhesive a obtained in Production Example 1 was applied to polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after evaporation (drying) of the solvent became 15 μm. film (thickness: 75 μm), and then dried to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The intermediate layer forming composition a obtained in Production Example 4 was applied to a polyethylene terephthalate film with a silicone release agent-treated surface so that the thickness after evaporation (drying) of the solvent became 15 μm. (manufactured by Toray, trade name "Cerapeel", thickness: 38 μm), and then dried 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 and bonded between rollers, and UV irradiation is performed from the intermediate layer precursor layer side under the condition of 500 mJ/cm ² to obtain the sandwiched tape Laminated body precursor layer a between polyethylene terephthalate films with silicone release agent-treated surfaces. The gas generating layer forming composition a obtained in Production Example 6 was applied to polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after evaporation (drying) of the solvent became 7 μm. film (manufactured by Toray Corporation, trade name "Cerapeel", thickness: 38 μm), and then 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 side of the intermediate layer precursor layer a of the above-mentioned laminated body precursor layer a, separate the intermediate layer precursor layer a of the laminated body precursor layer a and The above-mentioned gas generation layer precursor layer a is laminated between rollers to obtain an adhesive sheet (adhesive layer/middle) sandwiched between polyethylene terephthalate films with silicone release agent-treated surfaces. layer/gas generating layer). The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 3] The adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate film with a silicone release agent-treated surface (thickness: 75 μm), and then dried to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The intermediate layer forming composition b obtained in Production Example 5 was applied to a polyethylene terephthalate film with a silicone release agent-treated surface so that the thickness after evaporation (drying) of the solvent became 15 μm. (manufactured by Toray, trade name "Cerapeel", thickness: 38 μm), and then dried 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 rollers to obtain a film sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. The precursor layer b of the laminated body. The gas generating layer forming composition a obtained in Production Example 6 was applied to polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after evaporation (drying) of the solvent became 7 μm. film (manufactured by Toray Corporation, trade name "Cerapeel", thickness: 38 μm), and then 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 side of the intermediate layer precursor layer b of the above-mentioned laminated body precursor layer b, separate the intermediate layer precursor layer b of the laminated body precursor layer b and The above-mentioned gas generation layer precursor layer a is laminated between rollers to obtain an adhesive sheet (adhesive layer/middle) sandwiched between polyethylene terephthalate films with silicone release agent-treated surfaces. layer/gas generating layer). The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 4] The adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate film with a silicone release agent-treated surface (thickness: 75 μm), and then dried to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The gas generating layer forming composition a obtained in Production Example 6 was applied to polyethylene terephthalate with a silicone release agent-treated surface so that the thickness after evaporation (drying) of the solvent became 7 μm. film (manufactured by Toray Corporation, trade name "Cerapeel", thickness: 38 μm), and then 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 rollers and bonded to one side of a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror #2F51N", thickness: 2 μm). Then, the gas generation layer precursor layer a is laminated between rollers and bonded to the side of the polyethylene terephthalate film opposite to the adhesive layer precursor layer a. In this way, an adhesive sheet (adhesive layer/intermediate layer/gas generating layer) sandwiched between polyethylene terephthalate films with silicone release agent-treated surfaces is obtained. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 5] An adhesive sheet was obtained in the same manner as in Example 4, except that the gas generating layer forming composition b was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 6] An adhesive sheet was obtained in the same manner as in Example 4, except that the gas generating layer forming composition c was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 7] An adhesive sheet was obtained in the same manner as in Example 4, except that the gas generating layer forming composition d was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 8] An adhesive sheet was obtained in the same manner as in Example 4, except that the gas generating layer forming composition e was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 9] An adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the adhesive layer was 1 μm and the thickness of the gas generation layer was 10 μm. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 10] An adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the adhesive layer was 1 μm and the thickness of the gas generation layer was 15 μm. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 11] An adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the adhesive layer was 5 μm and the thickness of the gas generation layer was 5 μm. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 12] An adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the adhesive layer was 10 μm and the thickness of the gas generation layer was 5 μm. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 13] An adhesive sheet was obtained in the same manner as in Example 4, except that the gas generating layer forming composition f was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 14] An adhesive sheet was obtained in the same manner as in Example 4, except that the gas generating layer forming composition g was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 15] The gas generating layer forming composition h was applied to a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror S10") so that the thickness after the solvent evaporated (dried) became 20 μm, thickness: 50 μm) to form a gas generation layer. Next, the adhesive b was applied to a polyethylene terephthalate film (manufactured by Toray Corporation, trade name) with a silicone release agent-treated surface so that the thickness after the solvent evaporated (dried) became 10 μm. "Cerapeel" thickness: 38 μm) to form an adhesive layer. Then, the gas generating layer and the adhesive layer are laminated to obtain an adhesive sheet (adhesive layer/gas generating layer/base material) protected by a polyethylene terephthalate film with a silicone release agent-treated surface. ). The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Example 16] An adhesive sheet was obtained in the same manner as in Example 15, except that the gas generating layer forming composition i was used instead of the gas generating layer forming composition h. The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Example 17] The gas generating layer forming composition j was applied to a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror S10") so that the thickness after the solvent evaporated (dried) became 20 μm, thickness: 50 μm) to form a gas generation layer. Next, the adhesive a was applied to a polyethylene terephthalate film (manufactured by Toray Corporation, trade name) with a silicone release agent-treated surface so that the thickness after the solvent evaporated (dried) became 5 μm. "Cerapeel" thickness: 38 μm) to form an adhesive layer. Then, the gas generating layer and the adhesive layer are laminated to obtain an adhesive sheet (adhesive layer/gas generating layer/base material) protected by a polyethylene terephthalate film with a silicone release agent-treated surface. ). The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Example 18] An adhesive sheet was obtained in the same manner as in Example 17, except that the gas generating layer forming composition k was used instead of the gas generating layer forming composition j. 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 Example 6 Example 7 adhesive layer Adhesive Adhesive a Adhesive a Adhesive a Adhesive a Adhesive a Adhesive a Adhesive a Thickness[μm] 15 7 7 7 7 7 7 Water vapor transmission rate of adhesive layer [g/(m ² ·day)] 3435.3 4059.3 4059.3 4059.3 4059.3 4059.3 4059.3 middle layer Middle layer material - Intermediate layer forming composition a Intermediate layer forming composition b PET PET PET PET Thickness[μm] 0 15 15 2 2 2 2 Water vapor transmission rate of the middle layer [g/(m ² ·day)] - 1778 78 3450 3450 3450 3450 gas generating layer Gas generating layer material Composition a for gas generation layer formation Composition a for gas generation layer formation Composition a for gas generation layer formation Composition a for gas generation layer formation Composition b for forming gas generating layer Gas generating layer forming composition c Composition d for forming gas generating layer Thickness[μm] 7 7 7 7 7 7 7 Molecular weight of UV absorber 958.2 958.2 958.2 958.2 958.2 629.8 647.8 TGA10% weight reduction temperature [℃] 352.8 352.8 352.8 352.8 352.8 401.5 391.7 Maximum absorption wavelength of UV absorber 356nm 356nm 356nm 356nm 356nm 349 nm 336nm Elastic modulus Er(gas)[MPa] 2.55 2.55 2.55 2.55 2.49 2.51 2.58 LogEr(gas) 6.41 6.41 6.41 6.41 6.40 6.40 6.41 8.01×h(gas) ^-0.116 6.39 6.39 6.39 6.39 6.39 6.39 6.39 The ^lower limit value of the elastic modulus of the gas generating layer [MPa] calculated based on Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^{- 0.116} 2.46 2.46 2.46 2.46 2.46 2.46 2.46 7.66×h(gas) ^-0.092 6.40 6.40 6.40 6.40 6.40 6.40 6.40 The lower limit value of the elastic modulus of the gas generating layer [MPa] calculated based on Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^-0.092 2.54 2.54 2.54 2.54 2.54 2.54 2.54 7.52×h(gas) ^-0.081 6.42 6.42 6.42 6.42 6.42 6.42 6.42 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] 2.65 2.65 2.65 2.65 2.65 2.65 2.65 47.675×h(gas) ^-0.519 17.37 17.37 17.37 17.37 17.37 17.37 17.37 The upper limit value of the elastic modulus of the gas generating layer calculated from Log(Er(gas)×10 ⁶ )≦47.675×h(gas) ^-0.519 [MPa] 231,953,590,863 231,953,590,863 231,953,590,863 231,953,590,863 231,953,590,863 231,953,590,863 231,953,590,863 adhesive sheet Thickness[μm] twenty two 29 29 16 16 16 16 Gas generation characteristics Transmittance@360 nm[%] 0.01 0.02 0.00 0.01 0.05 0.00 0.20 Maximum gas generation peak temperature [℃] 380 370 370 380 380 390 395 Gasification starting temperature [℃] 335 330 330 335 335 360 370 gas species Hydrocarbon Hydrocarbon Hydrocarbon Hydrocarbon Hydrocarbon Hydrocarbon Hydrocarbon TGA5% weight reduction temperature [℃] 312.6 306.2 304.5 312.6 310.3 319.2 326.2 TGA10% weight reduction temperature [℃] 349.5 340.1 339.5 349.5 347.2 359.6 369.9 Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 3158.9 1238.1 198.1 334.2 330.2 328.4 339.4 Surface shape changes Height (Y: vertical displacement) 3.4 1.4 1.2 10.6 5.3 10.5 4.5 Diameter (X: horizontal displacement) 23.1 13.2 10.1 51.2 42.1 40.6 41.3 condition Foaming convex Foaming convex Foaming convex Foaming convex Foaming convex Foaming convex Foaming convex Adhesion force to SUS430 [N/20 mm] (adhesive layer side) 4.20 3.46 2.32 0.33 0.31 0.35 0.39 Adhesion force to SUS430 [N/20 mm] (gas generation layer side) 5.22 3.86 2.95 4.74 4.59 4.30 4.68 Peelability 〇 〇 〇 ◎ 〇 ◎ 〇 In-plane uniformity of deformation 〇 〇 〇 〇 〇 △ 〇 location selectivity 〇 〇 〇 〇 〇 〇 〇

[table 5] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 adhesive layer Adhesive Adhesive a Adhesive a Adhesive a Adhesive a Adhesive a Adhesive a Adhesive a Thickness[μm] 7 1 1 5 10 7 7 Water vapor transmission rate of adhesive layer [g/(m ² ·day)] 4059.3 6216.2 6216.2 4369.7 3754.3 4059.3 4059.3 middle layer Middle layer material PET PET PET PET PET PET PET Thickness[μm] 2 2 2 2 2 2 2 Water vapor transmission rate of the middle layer [g/(m ² ·day)] 3450 3450 3450 3450 3450 3450 3450 gas generating layer Gas generating layer material Composition e for forming gas generating layer Composition a for gas generation layer formation Composition a for gas generation layer formation Composition a for gas generation layer formation Composition a for gas generation layer formation Composition f for forming gas generating layer Composition g for forming gas generating layer Thickness[μm] 7 10 15 5 5 7 7 Molecular weight of UV absorber 315.8 958.2 958.2 958.2 958.2 958.2 958.2 TGA10% weight reduction temperature [℃] 234.5 352.8 352.8 352.8 352.8 352.8 352.8 Maximum absorption wavelength of UV absorber 355nm 356nm 356nm 356nm 356nm 356nm 356nm Elastic modulus Er(gas)[MPa] 2.50 2.55 2.55 2.55 2.55 3.14 1.49 LogEr(gas) 6.40 6.41 6.41 6.41 6.41 6.50 6.17 8.01×h(gas) ^-0.116 6.39 6.13 5.85 6.65 6.65 6.39 6.39 The ^lower limit value of the elastic modulus of the gas generating layer [MPa] calculated based on Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^{- 0.116} 2.46 1.36 0.71 4.42 4.42 2.46 2.46 7.66×h(gas) ^-0.092 6.40 6.20 5.97 6.61 6.61 6.40 6.40 The lower limit value of the elastic modulus of the gas generating layer [MPa] calculated based on Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^-0.092 2.54 1.58 0.93 4.03 4.03 2.54 2.54 7.52×h(gas) ^-0.081 6.42 6.24 6.04 6.60 6.60 6.42 6.42 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] 2.65 1.74 1.09 3.99 3.99 2.65 2.65 47.675×h(gas) ^-0.519 17.37 14.43 11.69 20.68 20.68 17.37 17.37 The upper limit value of the elastic modulus of the gas generating layer calculated from Log(Er(gas)×10 ⁶ )≦47.675×h(gas) ^-0.519 [MPa] 231,953,590,863 269,655,802 492,361 477,306,097,077,199 477,306,097,077,199 231,953,590,863 231,953,590,863 adhesive sheet Thickness[μm] 16 13 18 12 17 16 16 Gas generation characteristics Transmittance@360 nm[%] 7.56 -0.01 -0.01 -0.01 -0.01 0.02 0.01 Maximum gas generation peak temperature [℃] 250 380 380 380 380 380 380 Gasification starting temperature [℃] 215 335 335 335 335 335 335 gas species Hydrocarbons, halogen compounds hydrocarbon hydrocarbon hydrocarbon hydrocarbon hydrocarbon hydrocarbon TGA5% weight reduction temperature [℃] 245.6 313.7 311.2 312.9 312.1 313.2 309.7 TGA10% weight reduction temperature [℃] 284.3 348.7 347.6 349.8 349.2 351.4 349.7 Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 298.6 280.8 252.3 314.7 346.0 336.2 284.1 Surface shape changes Height (Y: vertical displacement) 8.2 10.4 6.0 7.0 4.5 6.5 15.7 Diameter (X: horizontal displacement) 36.4 72.6 49.1 59.7 41.8 39.3 41.5 condition Foaming convex Foaming convex Foaming convex Foaming convex Foaming convex Foaming convex Foaming convex Adhesion force to SUS430 [N/20 mm] (adhesive layer side) 1.05 0.21 0.19 0.32 0.46 0.46 0.42 Adhesion force to SUS430 [N/20 mm] (gas generation layer side) 0.58 4.80 5.41 4.31 4.38 2.52 6.37 Peelability ◎ ◎ 〇 〇 〇 〇 ◎ In-plane uniformity of deformation △ 〇 〇 〇 〇 △ △ location selectivity 〇 〇 〇 〇 〇 〇 〇

[Table 6] Example 15 Example 16 Example 17 Example 18 adhesive layer Adhesive Adhesive b Adhesive b Adhesive a Adhesive a Thickness[μm] 10 10 5 5 Water vapor transmission rate of adhesive layer [g/(m ²・day)] 3754.3 3754.3 4369.7 4369.7 middle layer Middle layer material - - - Thickness[μm] 0 0 0 0 Water vapor transmission rate of the middle layer [g/(m ²・day)] - - - gas generating layer Gas generating layer material Gas generating layer forming composition h Composition for forming gas generating layer i Gas generating layer forming compositionj Gas generating layer forming composition k Molecular weight of UV absorber 958.2 958.2 647.8 647.8 TGA10% weight reduction temperature [℃] 352.8 352.8 391.7 391.7 Maximum absorption wavelength of UV absorber 356nm 356nm 336nm 336nm Thickness h(gas)[μm] 20 20 20 20 Elastic modulus Er(gas)[MPa] 0.95 77.62 0.50 0.70 LogEr(gas) 5.98 7.89 5.70 5.85 8.01×h(gas) ^-0.116 5.66 5.66 5.66 5.66 The ^lower limit value of the elastic modulus of the gas generating layer [MPa] calculated based on Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^{- 0.116} 0.46 0.46 0.46 0.46 7.66×h(gas) ^-0.092 5.81 5.81 5.81 5.81 The lower limit value of the elastic modulus of the gas generating layer [MPa] calculated based on Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^-0.092 0.65 0.65 0.65 0.65 7.52×h(gas) ^-0.081 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 47.675×h(gas) ^-0.519 10.07 10.07 10.07 10.07 The upper limit value of the elastic modulus of the gas generating layer calculated from Log(Er(gas)×10 ⁶ )≦47.675×h(gas) ^-0.519 [MPa] 11765.71 11765.71 11765.71 11765.71 base material Base material PET PET PET PET Thickness[μm] 50 50 50 50 adhesive sheet Thickness[μm] 80 80 75 75 Gas generation characteristics Transmittance@360 nm[%] 0.21 0.21 11.28 25.25 Maximum gas generation peak temperature [℃] 375 365 390 395 Gasification starting temperature [℃] 330.0 325.0 360 370 gas species hydrocarbon hydrocarbon hydrocarbon Hydrocarbon TGA5% weight reduction temperature [℃] 320.4 318.9 335.7 341.0 TGA10% weight reduction temperature [℃] 352.8 349.0 364.1 365.1 Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 9.2 10.1 9.8 11.1 Surface shape changes Height (Y: vertical displacement) 1.8 4.3 0.7 0.6 Diameter (X: horizontal displacement) 18.3 20.5 12.1 9.8 condition Foaming convex Foaming convex Foaming convex Foaming convex Adhesion force to SUS430 [N/20 mm] (adhesive layer side) 0.69 0.25 1.52 1.76 Peelability 〇 〇 〇 〇 In-plane uniformity of deformation 〇 〇 〇 〇 location selectivity 〇 〇 〇 〇

[Comparative example 1] An adhesive sheet was obtained in the same manner as in Example 4, except that the gas generating layer forming composition I was used instead of the gas generating layer forming composition a. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 7.

[Comparative example 2] Adhesive I was used instead of adhesive a, the thickness of the adhesive layer was set to 10 μm, a PET film with a thickness of 188 μm was used as the intermediate layer, and a combination containing thermally expandable microspheres was used instead of gas generation layer forming composition a. Material I formed a gas generating layer of 48 μm, and an adhesive sheet was obtained in the same manner as in Example 4, except that a gas generating layer of 48 μm was formed. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 7.

[Comparative example 3] Adhesive I was used instead of Adhesive A, the thickness of the adhesive layer was set to 10 μm, a PET film with a thickness of 100 μm was used as the intermediate layer, and a combination containing thermally expandable microspheres was used instead of Gas Generating Layer Forming Composition A. Material II formed a gas generating layer of 48 μm, and an adhesive sheet was obtained in the same manner as in Example 4, except that a gas generating layer of 48 μm was formed. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 7.

[Table 7] Comparative example 1 Comparative example 2 Comparative example 3 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 Middle layer material PET PET PET Thickness[μm] 2 188 100 Water vapor transmission rate of the middle layer [g/(m ²・day)] 3450 - - gas generating layer Gas generating layer material Gas generating layer forming composition I Composition I containing thermally expandable microspheres Composition II containing thermally expandable microspheres Thickness[μm] 7 48 48 Molecular weight of UV absorber - - TGA10% weight reduction temperature [℃] - - Maximum absorption wavelength of UV absorber - - adhesive sheet constitute Thickness[μm] 16 246 158 Gas generation characteristics Transmittance@360 nm[%] 90.57 58.32 71.78 Maximum gas generation peak temperature [℃] 400 (from polymer) - - Gasification starting temperature [℃] 350 (from polymer) - - gas species hydrocarbon hydrocarbon hydrocarbon TGA5% weight reduction temperature [℃] 336.519 - - TGA10% weight reduction temperature [℃] 362.492 - - Gas barrier properties Water vapor transmission rate [g/(m ²・day)] 260.1 - - Surface shape changes Height (Y: vertical displacement) - ≧100 μm ≧100 μm Diameter (X: horizontal displacement) - ≧200 μm ≧200 μm condition Rupture × plural foaming convex plural foaming convex Adhesion force to SUS430 [N/20 mm] (adhesive layer side) 2.12 - - Adhesion force to SUS430 [N/20 mm] (gas generation layer side) 4.60 - - Peelability × ◎ ◎ In-plane uniformity of deformation - × × location selectivity 〇 × ×

4:Sample 5A, 5B: Sample holder 6: Compression testing machine 10: Gas generation layer 20: Adhesive layer 30:Middle layer 100,200: Adhesive sheet

FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention. FIG. 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 illustrating a method of measuring puncture strength.

10: Gas generation layer

20: Adhesive layer

100:Adhesive sheet

Claims (15)

An adhesive sheet having a gas generating layer and at least one adhesive layer disposed on one side of the gas generating layer. The adhesive layer is a layer whose surface is deformed by irradiating the adhesive sheet with laser light. , the gas generating layer is a layer that can absorb ultraviolet rays, and the gas generating layer contains an ultraviolet absorber. The adhesive sheet of claim 1, wherein the thickness of the gas generating layer is 0.1 μm ~ 50 μm. The adhesive sheet of claim 1, wherein the gas generating layer is a layer that generates hydrocarbon gas. For example, the adhesive sheet of claim 1, wherein the gasification starting temperature of the gas generating layer is 150°C to 500°C. The so-called gasification starting temperature of the gas generating layer refers to the gas released when the adhesive sheet is heated. The gas production rising temperature calculated by analysis (EGA analysis) is the temperature that reaches half the maximum gas production peak of the EGA/MS spectrum obtained by EGA analysis. The adhesive sheet of claim 1, wherein the elastic modulus Er (gas) [unit: MPa] and 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). Such as the adhesive sheet of claim 1, wherein the thickness of the above-mentioned adhesive layer is 0.1 μm ~ 50 μm. The adhesive sheet of Claim 1, wherein the deformation amount of the surface of the adhesive layer caused by irradiating the adhesive sheet with laser light is 0.6 μm or more in terms of the vertical displacement of the adhesive layer. For example, the adhesive sheet in claim 1 has an ultraviolet transmittance of less than 30% at a wavelength of 360 nm. For example, the adhesive sheet in claim 1 has a 10% weight loss temperature of 200°C to 500°C. The so-called 10% weight loss temperature refers to the 10% weight loss temperature of the gas generating layer, which is the heat when the adhesive sheet is heated. In gravimetric analysis (TGA analysis), the temperature is the temperature at which the weight of the gas generation layer decreases by 10% by weight relative to the weight before temperature rise. For example, the adhesive sheet in claim 1 has a water vapor transmission rate of 5000g/(m ² ‧day) or less. A method for processing electronic parts, which includes: attaching electronic parts to an adhesive sheet according to any one of claims 1 to 10; and irradiating the adhesive sheet with laser light to peel off the electronic components from the adhesive sheet. Component. A method for processing electronic parts as claimed in claim 11, wherein the stripping of the electronic parts is carried out at a selected location. For example, the processing method of electronic parts in claim 11 includes: After the electronic component is attached to the adhesive sheet and before the electronic component is peeled off from the adhesive sheet, the electronic component is subjected to specific processing. Such as the processing method of electronic parts in claim 13, wherein the above-mentioned processing is grinding processing, cutting processing, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer printing, arrangement, Repair or install surface protection. The method of processing electronic parts according to claim 11 includes: peeling off the electronic parts from the adhesive sheet, and arranging the electronic parts on another sheet.