TW202124639A - Adhesive sheet - Google Patents

Abstract

The present invention provides an adhesive sheet that can temporarily fix small electronic parts (for example, a chip with a size of 100 μm□ or less) and can be peeled off well. The adhesive sheet of the present invention is provided with a gas generating layer and at least one adhesive layer arranged on one side of the gas generating layer, and the adhesive layer is a layer 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 processing (processing) electronic parts, there were cases where the following operations were performed, that is, the processed object was temporarily fixed to the adhesive sheet during processing, and the processed object was peeled from the adhesive sheet after processing . As the adhesive sheet used in this operation, there are cases where the following adhesive sheet is used, which has a specific adhesive force during processing, and the adhesive force can be reduced after processing. As one of such adhesive sheets, there is proposed an adhesive sheet formed by including thermally expandable microspheres in an adhesive layer (for example, Patent Document 1). The adhesive sheet containing heat-expandable microspheres has the following characteristics: it has a specific adhesive force, and the heat-expandable microspheres are expanded by heating to form unevenness on the adhesive surface, thereby reducing the contact area, so the adhesive force will be reduced Or disappear. This kind of adhesive sheet has the advantage of being able to easily peel off the processed body without external stress.

However, in recent years, along with the trend toward lighter weights of various devices and an increase in the number of devices mounted, the miniaturization of electronic components has been promoted, and it has become necessary to temporarily fix electronic components that are downsized to the same size as the above-mentioned thermally expandable microspheres. . In the case of temporarily fixing electronic parts that have been miniaturized for processing, due to the particle size deviation, the influence of the parts where the thermally expandable microspheres with larger particle diameters and the parts where there are no heat-expandable microspheres becomes greater. There are situations where good peeling cannot be done in this part. Prior art literature Patent literature

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

[The problem to be solved by the invention]

The present invention was completed in order to solve the aforementioned problems, and its object is to provide an adhesive sheet that can temporarily fix small electronic parts (for example, a chip with a size of 100 μm□ or less) and can be peeled off well. [Technical means to solve the problem]

The adhesive sheet of the present invention is provided with a gas generating layer and at least one adhesive layer arranged on one side of the gas generating layer, and the adhesive layer is a layer whose surface is deformed by irradiating the adhesive sheet with laser light . In one embodiment, the 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 is 0.1 μm-50 μm. In one embodiment, the gas generating layer is a layer that generates hydrocarbon-based gas. In one embodiment, the gasification initiation temperature of the gas generating layer is 150°C to 500°C. In one embodiment, the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] of the gas generating layer obtained by the nanoindentation method satisfy the following formula (1). Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^-0.116 ...(1) In one embodiment, the thickness of the adhesive layer is 0.1 μm-50 μm. In one embodiment, the amount of deformation of the surface of the adhesive layer generated 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 adhesive sheet with a wavelength of 360 nm is 30% or less. In one embodiment, the 10% weight reduction temperature of the adhesive sheet is 200°C to 500°C. In one embodiment, the water vapor transmission rate of the adhesive sheet is 5000 g/(m ² ·day) or less. According to another aspect of the present invention, a processing method of electronic components is provided. The processing method of the electronic component includes: attaching the electronic component to the adhesive sheet; and irradiating the adhesive sheet with laser light to peel the electronic component from the adhesive sheet. In one embodiment, the peeling of the above-mentioned electronic components is performed at selected positions. In one embodiment, it includes: after the electronic component is attached to the adhesive sheet and before the electronic component is peeled from the adhesive sheet, specific processing is performed on the electronic component. In one embodiment, the above-mentioned processing is grinding processing, cutting processing, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer, arrangement, repair, or device surface protection. In one embodiment, the processing method of the electronic component includes: after peeling the electronic component from the adhesive sheet, arranging the electronic component on another sheet. [Effects of Invention]

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

A. Outline of Adhesive Sheet Fig. 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. In more detail, the gas generating layer 10 is a layer that generates gas by vaporizing its components by irradiation with laser light. 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 is generated on the side of the adhesive layer 20 opposite to the gas generation layer 10 due to the gas generated from the gas generation layer 10. As the laser light, UV (ultraviolet) laser light is typically used.

The adhesive sheet of the present invention can be used for attaching electronic parts and other objects to be processed on an adhesive layer. The adhesive sheet of the present invention is provided with a gas generating layer, and is irradiated with laser light to locally generate gas in a small area. As described above, due to the generation of the gas, the adhesive layer is deformed, and as a result, the part irradiated with the laser light exhibits releasability. Typically, the laser light is irradiated from the side of the gas generating layer opposite to the adhesive layer. According to the present invention, deformation can be generated in a small area as described above, and therefore, when processing (processing) an extremely fine small electronic component, the small electronic component can also be peeled off well. In addition, even when the small electronic parts that need to be peeled off are temporarily fixed adjacent to the small electronic parts that do not need to be peeled off, the peeling can be performed at the part of the peeling target, and the peeling is not performed at the part outside the peeling target, that is, you can Only the small electronic parts that need to be peeled off can also prevent unnecessary detachment of the small electronic parts. In order to produce good deformation of the adhesive layer, it is preferable to block at least a part of the generated gas not to escape from the adhesive sheet, and the adhesive layer can function as a gas barrier layer. In addition, the adhesive sheet has excellent directivity at the time of peeling, and it can be peeled only at a desired location, and it is also advantageous in terms of preventing breakage and having less paste residue. Furthermore, the directivity at the time of peeling refers to the index of the positional accuracy when the adherends such as small electronic parts are peeled from the adhesive sheet and aligned at a certain distance away from the adhesive sheet. If the directivity is excellent, then Prevent the adherend from flying out of the expected direction during peeling.

之UV雷射光，於0.80 mW功率、40 kHz頻率下進行脈衝掃描，而自氣體產生層產生氣體。關於變形後之形狀，例如對於脈衝掃描過之任意1點，於雷射光照射結束1分鐘後，根據共聚聚焦雷射顯微鏡或非接觸型干涉顯微鏡(WYKO)等之測定進行觀測。其形狀可為發泡(凸狀)、貫通孔(凹凸狀)、凹陷(凹狀)，藉由該等變形而可產生剝離性。於要沿法線方向將電子零件效率良好地剝離時，較佳為雷射光照射前後之法線方向之位移變化較大，尤其適合形成發泡形狀者。發泡(凸狀)係以未照射部之黏著片材表面為基準，將最高點定義為垂直位移Y，將半峰全幅值定義為水平位移X(直徑)。關於雷射光照射後形成孔之貫通孔(凹凸)與凹陷(凹)，將最高點與最低點之差定義為垂直位移Y，將孔之直徑定義為水平位移X。以下，亦將藉由雷射光照射而變形之部分稱為｢變形部｣。黏著劑層之垂直位移較佳為0.6 μm以上，更佳為0.7 μm以上，進而較佳為1.0 μm以上。若為此種範圍，則剝離性優異，剝離時之指向性優異。又，可向所需方向精度良好地剝離，其結果，可防止糊劑殘留、破損等。該垂直位移之上限例如為10 μm(較佳為20 μm)。黏著劑層之水平位移較佳為80 μm以下，更佳為50 μm以下，進而較佳為40 μm以下。若為此種範圍，則對於較小之被黏著體，可較佳地進行僅於需要部位之剝離。又，於被黏著體以較窄間隔排列之情形時，亦可期待同樣之效果。該水平位移之下限例如為3 μm(較佳為4 μm)。The so-called deformation of the adhesive layer refers to the displacement generated in the normal direction (thickness direction) and the horizontal direction (direction orthogonal to the thickness direction) of the adhesive layer. The deformation of the adhesive layer is produced by, for example, the following method: by using a wavelength of 355 nm and a beam diameter of about 20 μm

The UV laser light is pulsed at 0.80 mW power and 40 kHz frequency, and gas is generated from the gas generating layer. Regarding the deformed shape, for example, for any one point scanned by the pulse, one minute after the laser light is irradiated, it is observed by measurement by a confocal laser microscope or a non-contact interference microscope (WYKO). The shape can be foamed (convex), through-hole (concave-convex), concave (concave), and releasability can be produced by these deformations. When the electronic parts are to be peeled off efficiently in the normal direction, it is preferable that the displacement in the normal direction before and after the laser light irradiation has a large change, and it is especially suitable for the foamed shape. Foaming (convex) is based on the surface of the non-irradiated part of the adhesive sheet, the highest point is defined as the vertical displacement Y, and the full width at half maximum is defined as the horizontal displacement X (diameter). Regarding the through-hole (concave-convex) and depression (concave) forming the hole after the laser light is irradiated, 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 the irradiation of laser light is also referred to as "deformation part". The vertical displacement of the adhesive layer is preferably 0.6 μm or more, more preferably 0.7 μm or more, and still more preferably 1.0 μm or more. If it is this range, the peelability will be excellent, and the directivity at the time of peeling will be excellent. In addition, it can be peeled accurately in a desired direction, and as a result, paste residue, breakage, 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 still more preferably 40 μm or less. If it is in such a range, for a small adherend, it is better to perform peeling only at the required part. In addition, when the adherends are arranged at narrow intervals, the same effect can be expected. 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 the intermediate layer, the deformation of the adhesive layer can be easily controlled (details are 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 are 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, the above-mentioned adhesive sheet may further include other layers. For example, a base material, another adhesive layer, etc. may be provided on the surface of the gas generating layer on the opposite side to the adhesive layer. As the substrate, 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～50 N/20 mm, and more preferably 0.5 N/20 mm ～40 N/20 mm, particularly preferably 0.7 N/20 mm～20 N/20 mm, most preferably 1 N/20 mm～10 N/20 mm. If it is in this range, for example, an adhesive sheet exhibiting good adhesiveness as a temporary fixing sheet used in the manufacture of electronic parts can be obtained. In this manual, the so-called adhesive force refers to the method in accordance with JIS (Japanese Industrial Standards) Z 0237:2000 under an environment of 23°C (fitting conditions: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180°) and the adhesive force measured.

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

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

The haze value of the adhesive sheet of the present invention is preferably 50% or less, more preferably 0.1% to 40%, and still more preferably 0.5% to 30%. If it is in this range, the adhered body can be visually recognized through the adhesive sheet (for example, a table for temporarily fixing electronic parts), so that, for example, a mark set on the fixing table for displaying the temporarily fixed position of the electronic part can be obtained. Adhesive sheet with excellent visibility. The adhesive sheet of the present invention can be constituted by not containing insoluble fillers in each layer of the adhesive sheet, and therefore can be an adhesive sheet with a small haze value and excellent visibility of the adhered as described above. This effect is an excellent effect that cannot be obtained with adhesive sheets containing insoluble fillers (for example, thermally expandable microspheres).

The water vapor transmission rate of the adhesive sheet of the present invention is preferably 5000 g/(m ² ·day) or less, more preferably 4800 g/(m ² ·day) or less, and still more preferably 4500 g/(m ² ·day) day) or less, more preferably 4200 g/(m ² ·day) or less. In an adhesive sheet with a water vapor transmission rate in this range, the escape of gas generated by laser light irradiation is prevented, and a deformed portion with an excellent shape is formed on the adhesive layer. If such an adhesive sheet is used, a small adherend (for example, an electronic component) can be peeled off accurately. The lower the water vapor transmission rate of the adhesive sheet of the present invention, the better, and the lower limit is, for example, 0.1 g/(m ² ·day). The water vapor transmission rate can be measured under an environment of 30°C and 90% RH by the measurement method in accordance with JIS K7129B.

The water vapor transmission rate of the laminate comprising the adhesive layer and the intermediate layer is preferably 10000 g/(m ² ·day) or less, more preferably 7000 g/(m ² ·day) or less, and still more preferably 5000 g /(m ² ·day) or less, more preferably 4800 g/(m ² ·day) or less, still more preferably 4500 g/(m ² ·day) or less, particularly ^{preferably 4200 g/(m 2} ·day) )the following. If it is in this range, the laminate including the adhesive layer and the intermediate layer functions well as a gas barrier layer, and a deformed portion with an excellent shape is formed in the adhesive layer. If such an adhesive sheet is used, a small adherend (for example, an electronic component) can be peeled off accurately. The lower the water vapor transmission rate of the laminate including the adhesive layer and the intermediate layer, the better, and the lower limit is, for example, 1 g/(m ² ·day).

The puncture strength of the laminate comprising the adhesive layer and the intermediate layer is preferably 10 mN～5000 mN, more preferably 30 mN～4000 mN, still more preferably 50 mN～3000 mN, especially preferably 100 mN～2000 mN. If it is in this range, the laminate including the adhesive layer and the intermediate layer functions well as a gas barrier layer, and the shape change caused by the generation of gas is preferably generated. As a result, the adhesive layer is formed Deformation of excellent shape. If such an adhesive sheet is used, a small adherend (for example, an electronic component) can be peeled off accurately. The puncture strength is shown in Figure 3. Using a compression tester 6 (manufactured by Kato Tech, trade name "KES-G5"), sample 4 (e.g., laminate) is sandwiched between a circular opening with a diameter of 11.28 mm. The sample holders 5A and 5B are used for the measurement. In more detail, the sample can be punctured (puncture speed: 0.1 mm/s) with a puncture needle (radius of curvature: 1 mm) at the center of the circular opening at the measurement temperature of 23°C. The maximum load at the rupture point is used 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%-100%, more preferably 60%-95%.

The ultraviolet transmittance of the adhesive sheet with 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 with 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, still more preferably 250°C to 400°C, and particularly preferably 270°C to 370°C. If it is in this range, it is possible to obtain an adhesive sheet that can form a better deformed portion by irradiation with laser light. The so-called 10% weight reduction temperature of the adhesive sheet means that in the TGA analysis when the temperature of the adhesive sheet is raised, it is reduced by 10% by weight relative to the weight before the temperature rise (that is, the weight of the adhesive sheet becomes 90% relative to the weight before irradiation. %) the temperature at the point in time.

B. Gas generating layer The gas generating layer can be a layer that can absorb ultraviolet rays. In one embodiment, the gas generating layer contains an ultraviolet absorber. By containing an ultraviolet absorber, a gas generating layer that can absorb laser light and vaporize can be formed. Typically, the gas generating layer contains an ultraviolet absorber and an adhesive A. It is preferable that the ultraviolet absorber is dissolved in the adhesive A and exists. If the ultraviolet absorber is dissolved in the adhesive A and exists, the following adhesive sheet can be obtained, which can produce deformed parts (for example, uneven parts) in any part of the adhesive layer, and the shape of the deformed parts (for example, uneven parts) The deviation is less. If such an adhesive sheet is used, a deformed portion (for example, uneven portion) can be accurately generated at a desired location, and the effect of the present invention becomes remarkable. In addition, in this specification, the state of "dissolved in an adhesive" means that the ultraviolet absorber is not present in the gas generating layer in the form of particles. More specifically, the gas generating layer preferably does not contain an ultraviolet absorber with a particle size of 10 μm or more in the particle distribution measurement in the cross section of the gas generating layer by X-ray CT (computer tomography). Furthermore, the gas generating layer may or may not contain insoluble components in the adhesive. In one embodiment, the presence and content of insoluble components in the gas generating layer is evaluated by the haze value of the gas generating layer. The smaller the haze value, the less the content of insoluble components in the gas generating layer is evaluated. It is preferable that the gas generating layer contains substantially no insoluble components in the adhesive.

The elastic modulus of the cross section of the gas generating layer obtained by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. If it is in this range, the shape change of the gas generating layer caused by the generation of gas is preferably generated. As a result, a deformed portion with an excellent shape is formed in the adhesive layer. The so-called modulus of elasticity obtained by the nanoindentation method refers to the continuous measurement of the load and the indentation depth of the indenter when the indenter is pressed into the sample (for example, the adhesion surface) when the indenter is pressed into the sample (for example, the adhesion surface) when spanning and unloading. And calculate the elastic modulus according to the obtained load-indentation depth curve. The modulus of elasticity obtained by the nanoindentation method is obtained as follows: For the displacement obtained by pressing a diamond-made Berkovich type (triangular pyramid type) probe vertically against the section cut out of the measurement target layer- The load hysteresis curve is processed numerically using the software (triboscan) attached to the measuring device. In this manual, the so-called elastic modulus of the cross-section obtained by the nanoindentation method is using a nanoindenter (Triboindenter TI-950 manufactured by Hysitron Inc.) by a single indentation at a specific temperature (25℃) Method, the elastic modulus measured under the measuring conditions of about 500 nm/sec of indentation speed, about 500 nm/sec of extraction speed, and about 1500 nm of indentation depth. 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, and the type and amount of additives added to the layer. Furthermore, in this specification, when the section or surface is not mentioned but only the modulus of elasticity obtained by the nanoindentation method is described, the modulus of elasticity refers to the modulus of elasticity obtained by the nanoindentation method of the section.

The elastic modulus of the surface of the gas generating layer obtained by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. If it is in this range, the shape change of the gas generating layer caused by the generation of gas is preferably generated. As a result, a deformed portion with an excellent shape is formed in the adhesive layer. The so-called modulus of elasticity obtained by the nanoindentation method refers to the continuous measurement of the load and the indentation depth of the indenter when the indenter is pressed into the sample (for example, the adhesion surface) when the indenter is pressed into the sample (for example, the adhesion surface) when spanning and unloading. And calculate the elastic modulus according to the obtained load-indentation depth curve. The modulus of elasticity obtained by the nanoindentation method is obtained as follows: For the displacement-load hysteresis curve obtained by pressing a diamond-made Berkovich (triangular pyramid) probe vertically against the measurement target layer, Use the software (triboscan) attached to the measuring device for numerical processing. In this manual, the so-called surface modulus of elasticity obtained by nanoindentation is using a nanoindenter (Triboindenter TI-950 manufactured by Hysitron Inc.) by a single indentation at a specific temperature (25℃) Method, the elastic modulus measured under the measurement conditions of an indentation speed of about 500 nm/sec, an extraction 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, and the type and amount of additives added to the layer. In the present invention, the elastic modulus obtained by the nanoindentation method measured by the above method using the cross section as the measurement surface, and the elastic modulus obtained by the nanoindentation method 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 the self-section, the value measured from the surface can be used as the measured value of the self-section.

The gasification initiation temperature of the gas generating layer is preferably 150°C to 500°C, more preferably 170°C to 450°C, still more preferably 190°C to 420°C, and particularly preferably 200°C to 400°C. If it is in this range, it is possible to obtain an adhesive sheet that can form a better deformed portion by irradiation with laser light. Furthermore, in this specification, the gasification initiation temperature of the gas generating layer refers to the gas generation temperature rise calculated based on the EGA analysis (evolved gas analysis) when the adhesive sheet is heated up. The so-called gas generation rising temperature is defined as the temperature that reaches the half value of the maximum gas generation peak of the EGA/MS spectrum obtained by EGA analysis. The lower the gasification initiation temperature, the lower the temperature at which gas will start to be generated when the laser light is irradiated, and a sufficient amount of gas will be generated when the laser light is irradiated with a smaller power. In one embodiment, the vaporization start temperature of the gas generating layer is equivalent to the vaporization start temperature of the ultraviolet absorber.

The 10% weight reduction temperature of the gas generating layer is preferably 150°C to 500°C, more preferably 170°C to 450°C, and still more preferably 200°C to 400°C. If it is in this range, it is possible to obtain an adhesive sheet that can form a better deformed portion by irradiation with laser light. The so-called 10% weight reduction temperature of the gas generating layer refers to the TGA analysis (thermogravimetric analysis) when the temperature of the adhesive sheet is raised (for example, when the temperature is raised by laser light irradiation), the weight of the gas generating layer is relative to the temperature rising The temperature at the time when the previous weight is reduced by 10% by weight (that is, the weight of the gas generating layer becomes 90% with respect to the weight before the temperature rise).

The thickness of the gas generating layer is preferably 0.1 μm-50 μm, more preferably 1 μm-40 μm, still more preferably 2 μm-30 μm, and particularly preferably 5 μm-20 μm. If it is in this range, it is possible to obtain an adhesive sheet that can form a better deformed portion by irradiation with laser light.

The elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] of the gas generating layer obtained by the nanoindentation method satisfy the following formula (1). Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^-0.116・・・(1) In the present invention, the gas generating layer is formed in a manner that satisfies the above formula (1) to prevent the gas Excessive deformation caused by gas generated in the generating layer, so that the adhesive sheet is well deformed by laser light irradiation. By forming such a gas generating layer, a thicker barrier layer (adhesive layer) is not required as a layer to prevent excessive deformation, and surface deformation within a small range can be generated, and an 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 this range, the said effect will become 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 with 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 still more preferably 0.5% to 40%.

B-1. Ultraviolet absorber As the ultraviolet absorber, any appropriate ultraviolet absorber can be used as long as the effects of the present invention are obtained. As the ultraviolet absorber, for example, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a tris-based ultraviolet absorber, a salicylate-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber may be mentioned. Absorbents, etc. Among them, tris-based ultraviolet absorbers or benzotriazole-based ultraviolet absorbers are preferred, and tris-based ultraviolet absorbers are particularly preferred. Especially when an acrylic adhesive is used as the adhesive A, the three UV absorbers have high compatibility with the base polymer of the acrylic adhesive, so they can be used preferably. The tri-type ultraviolet absorber is more preferably a compound having a hydroxyl group, and more preferably a hydroxyphenyl tri-type compound (hydroxyphenyl tri-type ultraviolet absorber).

As a hydroxyphenyl tris-based ultraviolet absorber, for example, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl)- The 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-tris glycidic acid (2-ethylhexyl) The ester reaction product (trade name "TINUVIN 405", manufactured by BASF Corporation), 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl) -1,3,5-tris (trade name "TINUVIN 460", manufactured by BASF), 2-(4,6-diphenyl-1,3,5-tris-2-yl)-5-[ (Hexyl)oxy]phenol (trade name "TINUVIN 1577", manufactured by BASF Corporation), 2-(4,6-diphenyl-1,3,5-tris-2-yl)-5-[2- (2-Ethylhexyloxy)ethoxy]phenol (trade name "Adekastab LA-46", manufactured by ADEKA Co., Ltd.), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy Phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-tris (trade name "TINUVIN 479", manufactured by BASF), trade name "TINUVIN 477" manufactured by BASF "Wait.

As a benzotriazole-based ultraviolet absorber (benzotriazole-based compound), for example, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (trade name " TINUVIN PS", manufactured by BASF Corporation), phenylpropionic acid, and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side Chain and linear alkyl) ester compounds (trade name "TINUVIN 384-2", manufactured by BASF Corporation), 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]propionate 2-ethylhexyl acid mixture (trade name "TINUVIN 109", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1- Phenylethyl)phenol (trade name "TINUVIN 900", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)- 4-(1,1,3,3-tetramethylbutyl)phenol (trade name "TINUVIN 928", manufactured by BASF), 3-(3-(2H-benzotriazol-2-yl)-5- The reaction product of methyl tert-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 (trade name "TINUVIN 1130", manufactured by BASF), 2-(2H-benzotriazol-2-yl) ) P-cresol (trade name "TINUVIN P", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol (trade name "TINUVIN 234", manufactured by BASF Corporation), 2-[5-chloro-2H-benzotriazol-2-yl]-4-methyl-6-(tertiary 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 Corporation), 2,2'- Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (trade name "TINUVIN 360", manufactured by BASF ), 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) methyl propionate and the reaction product of polyethylene glycol 300 (trade name " TINUVIN 213", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (trade name "TINUVIN 571", BASF Company manufacture), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthaliminomethyl)-5-methylphenyl]benzotriazole (trade name "Sumisorb 250", manufactured by Sumitomo Chemical Co., Ltd.), 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole (trade name "SEESORB 703", manufactured by Shipro Kasei), 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimino Methyl)phenol (trade name "SEESORB 706", manufactured by Shipro Kasei), 2-(4-benzyloxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole (Shipro Kasei) Manufactured with the trade name "SEESORB 7012BA"), 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (trade name "KEMISORB 73", Chemipro Kasei Corporation), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tertiary octylphenol] (trade name "Adekastab LA-31", ADEKA shares Co., Ltd.), 2-(2H-benzotriazol-2-yl)p-cresol (trade name "Adekastab LA-32", manufactured by ADEKA Co., Ltd.), 2-(5-chloro-2H-benzo Triazol-2-yl)-6-tert-butyl-4-methylphenol (trade name "Adekastab LA-36", manufactured by ADEKA Co., Ltd.) and the like.

The molecular weight of the compound constituting the aforementioned ultraviolet absorber is preferably 200-1500, more preferably 250-1200, and still more preferably 300-1000. If it is in this range, it is possible to obtain an adhesive sheet that can form a better deformed portion by irradiation with laser light.

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

With respect to 100 parts by weight of the gas generating layer, the content of the ultraviolet absorber is preferably 1 part by weight to 100 parts by weight, more preferably 1 part by weight to 50 parts by weight, and still more preferably 5 parts by weight to 30 parts by weight. If it is in this range, it is possible to obtain an adhesive sheet that can form a better deformed portion by irradiation with laser light.

B-2. Adhesive A As the adhesive A contained in the gas generating layer, a pressure-sensitive adhesive A is preferably used. As the adhesive A, for example, acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, amine based adhesives 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 said adhesive can be used individually or in combination of 2 or more types.

As the above-mentioned acrylic adhesive, for example, an acrylic polymer (homopolymer or copolymer) using one or two or more of alkyl (meth)acrylates as a monomer component is used as a base polymer. Acrylic adhesives, etc. Specific examples of alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary 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 Yl)isononyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, (meth) Tridecyl acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate , Stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate and other (meth)acrylate C1-20 alkyl esters. Among them, alkyl (meth)acrylates having a linear or branched alkyl group having 4 to 18 carbon atoms can be preferably used.

The aforementioned acrylic polymer can also be used for the purpose of modification of cohesive force, heat resistance, crosslinkability, etc., and optionally contains units corresponding to other monomer components copolymerizable with the aforementioned alkyl (meth)acrylate. Examples of such monomer components include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. The monomers; anhydride monomers such as maleic anhydride and itaconic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, (meth)acrylic acid Hydroxyhexyl ester, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate and other hydroxyl-containing monomers Body; styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide propanesulfonic acid, (meth)sulfopropyl acrylate , (Meth)acryloxynaphthalenesulfonic acid and other monomers containing sulfonic acid groups; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, (N-substituted) amide monomers such as acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc.; (meth)acrylamide (Meth)acrylic acid aminoalkyl ester monomers such as methacrylic acid ethyl ester, (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid tertiary butylaminoethyl ester, etc.; Alkoxyalkyl (meth)acrylate monomers such as methoxyethyl methacrylate and ethoxyethyl (meth)acrylate; N-cyclohexyl maleimide, N- Maleimide monomers such as isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide, etc.; N-methyl Ikonimines, N-ethyl Ikonimines, N-Butyl Ikonimines, N-octyl Ikonimines, N-2-Ethylhexyl Ikonimines, N -Cyclohexyl Ikonimines, N-Lauryl Ikonimines and other Ikonimines monomers; N-(meth)acryloxymethylene succinimide, N-( Meth) acryloyl-6-oxyhexamethylene succinimide, N-(meth) acryloyl-8-oxy octamethylene succinimide, etc. Monomers; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidine, vinyl Pyridine, vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl pyridine, N-vinylcarboxamides, styrene, α-methylstyrene, N-vinyl caprolactam and other ethylene Base monomers; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; glycidyl (meth)acrylate and other epoxy-containing acrylic monomers; (meth)acrylate polyethylene glycol, ( Meth) acrylic propylene glycol, (meth) acrylic methoxy glycol, (meth) acrylic methoxy polypropylene glycol and other glycol-based acrylate monomers; (meth) acrylic tetrahydrofuran methyl, fluorine (form) Base) acrylate, silicone (meth)acrylate and other acrylate monomers having heterocycles, halogen atoms, silicon atoms, etc.; hexanediol di(meth)acrylate, (poly)ethylene glycol di( Meth) acrylate, (poly)propylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate , Dipentaerythritol hexa(meth)acrylate, epoxy acrylate, acrylic polyester, acrylic urethane and other multifunctional monomers; isoprene, butadiene, isobutylene and other olefin monomers; vinyl ether And other vinyl ether monomers. These monomer components can be used individually or in combination of 2 or more types.

As the above-mentioned rubber-based adhesives, for example, rubber-based adhesives using the following as the base polymer can be exemplified: 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, reclaimed rubber, butadiene rubber Synthetic rubbers such as base rubber, polyisobutylene, these modified products, etc.

The gas generated from the above-mentioned gas generating layer is preferably a hydrocarbon (preferably aliphatic hydrocarbon)-based gas. The gas generating layer capable of generating hydrocarbon-based gas is composed of, for example, a hydrocarbon-based compound as a main component. The gas generating layer preferably does not contain a halogen-containing compound. If the generated gas is a hydrocarbon-based gas, it can prevent the corrosion of electronic parts that are processed. This effect becomes more pronounced by forming a gas generating layer that does not contain halogen-containing compounds. The amount of ion generated from the gas generating layer is preferably 10 m/z～800 m/z, more preferably 11 m/z～700 m/z, and still more preferably 12 m/z～500 m/z, especially Preferably, it is 13 m/z to 400 m/z.

The above-mentioned adhesive A may optionally contain any appropriate additives. Examples of the additives include crosslinking agents, adhesion-imparting agents (for example, rosin-based adhesion-imparting agents, terpene-based adhesion-imparting agents, hydrocarbon-based adhesion-imparting agents, etc.), plasticizers (for example, trimellitic acid Ester plasticizers, pyromellitic acid ester plasticizers), pigments, dyes, anti-aging agents, conductive materials, antistatic agents, light stabilizers, peeling regulators, softeners, surfactants, flame retardants Agents, antioxidants, etc.

Examples of the above-mentioned crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, and metal alkoxide-based crosslinking agents. Cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, azoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking剂 etc. Among them, an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent is preferred.

Specific examples of the above-mentioned isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; 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"), isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "Coronate HX") and other isocyanate adducts. The content of the isocyanate-based crosslinking agent can be set to any appropriate amount according to the required adhesive force, and is typically 0.1 to 20 parts by weight, more preferably 0.5 parts by weight relative to 100 parts by weight of the base polymer ~10 parts by weight.

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

C. Adhesive layer The above-mentioned adhesive layer contains any suitable adhesive B. As the adhesive B, it may be a pressure-sensitive adhesive B1 or a hardening type adhesive B2.

The thickness of the adhesive layer is preferably 0.1 μm-50 μm, more preferably 0.5 μm-40 μm, still more preferably 1 μm-30 μm, and particularly preferably 2 μm-20 μm. If it is in this range, it is possible to form an adhesive layer that has a better adhesive force and functions well as a gas barrier layer.

The water vapor transmission rate of the adhesive layer is preferably 20,000 g/(m ² ·day) or less, more preferably 10,000 g/(m ² ·day) or less, and still more preferably 7000 g/(m ² ·day) Hereinafter, it is more preferably 5000 g/(m ² ·day) or less, still more preferably 4800 g/(m ² ·day) or less, and particularly ^{preferably 4500 g/(m 2} ·day) or less. If it is in this range, the adhesive layer functions well as a gas barrier layer and forms a deformed portion with an excellent shape. If such an adhesive sheet is used, a small adherend (for example, an electronic component) can be peeled off accurately. The lower the water vapor transmission rate of the adhesive layer, the better, and the lower limit is, for example, 100 g/(m ² ·day).

The puncture strength of the adhesive layer is preferably 10 mN to 3000 mN, more preferably 30 mN to 2500 mN, still more preferably 50 mN to 2000 mN, and particularly preferably 100 mN to 2000 mN. If it is in this range, the adhesive layer functions well as a gas barrier layer, and the shape change caused by the generation of gas is preferably generated. As a result, a deformed portion with an excellent shape is formed. If such an adhesive sheet is used, a small adherend (for example, an electronic component) can be peeled off accurately.

The ultraviolet transmittance of the adhesive layer with a wavelength of 360 nm is preferably 50%-100%, more preferably 60%-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-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. 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 As the curable adhesive B2, for example, a thermosetting adhesive, an active energy ray curable adhesive, etc. may be mentioned. It is preferable to use an active energy ray-curable adhesive. The adhesive layer formed by the active energy ray hardening adhesive is an adhesive layer formed by irradiating active energy rays, that is, an adhesive layer having a specific adhesive force after the active energy ray is irradiated.

As the resin material constituting the active energy ray-curable adhesive, for example, ultraviolet curing system (by Kato Kiyoshi, published by Comprehensive Technology Center (1989)), photocuring technology (edited by the Technical Information Association (2000)), A resin material described in Japanese Patent Laid-Open No. 2003-292916, Japanese Patent No. 4151850, etc. More specifically, a resin material (B2-1) containing a polymer that becomes a master agent and an active energy ray reactive compound (monomer or oligomer), and a resin material containing an active energy ray reactive polymer can be exemplified (B2-2) and so on.

As the above-mentioned polymer that becomes the master agent, for example, natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, reclaimed rubber, butyl Rubber, polyisobutylene rubber, nitrile rubber (NBR (Nitrile Butadiene Rubber)) and other rubber-based polymers; silicone-based polymers; acrylic-based polymers, etc. These polymers can be used individually or in combination of 2 or more types.

As the above-mentioned active energy ray reactive compound, for example, a photoreactive compound containing a plurality of functional groups having carbon-carbon multiple bonds such as acrylic groups, methacrylic groups, vinyl groups, allyl groups, and ethynyl groups can be mentioned. 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. The compound having an ethylenically unsaturated functional group easily generates free radicals by ultraviolet rays. Therefore, if the compound is used, an adhesive layer that can be cured in a short time can be formed. In addition, 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 photoreactive monomers or oligomers include: trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(methyl) ) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, Compounds containing (meth)acrylic acid groups such as 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, (meth)acrylate urethane compounds, etc. ; The dimer ~ pentamer of the (meth)acrylic acid group-containing compound. These compounds can be used individually or in combination of 2 or more types.

In addition, as the active energy ray reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinyl silicone; or oligomers composed of such monomers can be used. Resin materials (B2-1) containing these compounds can be cured 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. The mixture is irradiated with active energy rays (for example, ultraviolet rays, electron beams), and organic salts are split to generate ions, which become the starting species to initiate the ring-opening reaction of the heterocyclic ring, thereby forming a three-dimensional network structure. Examples of the above-mentioned organic salts include phosphonium 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 polymer used as the master agent and the active energy ray reactive compound, the content ratio of the active energy ray reactive compound relative to 100 parts by weight of the polymer used as the master agent is preferably 0.1 Parts by weight to 500 parts by weight, more preferably 1 part by weight to 300 parts by weight, and still more preferably 10 parts by weight to 200 parts by weight.

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

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 active energy ray-curable adhesive can be cured by irradiation of active energy rays. In the adhesive sheet of the present invention, after the adherend is attached before the adhesive is hardened, active energy rays are irradiated to harden the adhesive, thereby allowing the adherend to be closely adhered. Examples of active energy rays include γ rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio frequency waves, α rays, β rays, electron beams, plasma flow, ionizing radiation, particle beams, and the like. The conditions such as the wavelength and irradiation amount of the active energy rays can be set to any appropriate conditions according to the type of resin material used, etc. For example, the adhesive can be cured by irradiating ultraviolet rays with an irradiation amount of 10 to 1000 mJ/cm ^2.

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

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

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

The water vapor transmission rate of the intermediate layer 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) or less , And more preferably 4200 g/(m ² ·day) or less. If it is in this range, the intermediate layer functions well as a gas barrier layer, and a deformed portion with an excellent shape is formed. If such an adhesive sheet is used, a small adherend (for example, an electronic component) can be peeled off accurately. The lower the water vapor transmission rate of the intermediate layer, the better, and the lower limit is, for example, 0.1 g/(m ² ·day).

The puncture strength of the intermediate layer is preferably 300 mN to 5000 mN, more preferably 500 mN to 4500 mN, and still more preferably 1000 mN to 4000 mN. If it is in this range, the intermediate layer functions well as a gas barrier layer, and the shape change caused by the generation of gas is preferably generated, and as a result, a deformed portion with an excellent shape is formed. If such an adhesive sheet is used, a small adherend (for example, an electronic component) can be peeled off accurately.

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

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

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

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

The thickness of the intermediate layer as the 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. Regarding the adhesive sheet of the present invention, for example, the following method can be exemplified: a composition for forming a gas generating layer containing adhesive A and an ultraviolet absorber is directly coated on a specific substrate to form a gas generating layer, and the gas is generated The adhesive layer forming composition containing adhesive B is coated 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 coated on the gas generating layer to form an intermediate layer, and the intermediate layer is coated The composition for forming an adhesive layer is applied to form an adhesive layer. Moreover, after forming each layer separately, you may bond together and form an adhesive sheet.

As the coating method of the above-mentioned composition, any appropriate coating method can be adopted. For example, drying can be performed after coating to form each layer. As the coating method, for example, a coating method using a multi-roll coater, a die-nozzle coater, a gravure coater, an applicator, or the like can be mentioned. As a drying method, natural drying, heat drying, etc. are mentioned, for example. In the case of heating and drying, the heating temperature can be set to any appropriate temperature according to the 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 the 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 Capacitor), and the like.

The peeling of the above-mentioned electronic parts can be carried out selectively. Specifically, attaching and fixing a plurality of electronic parts to the adhesive sheet can peel off a part of the electronic parts while keeping other electronic parts fixed.

In one embodiment, the processing method of the electronic component of the present invention includes: after the electronic component is attached to the adhesive sheet and before the electronic component is peeled from the adhesive sheet, specific processing is performed on the electronic component. The above treatment is not particularly limited, and examples include: grinding, cutting, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, product inspection, cleaning, transfer, arrangement, repair, equipment 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 250,000 μm ² . In one embodiment, the size of the electronic component (the area of the attachment surface) is 1 μm ² to 6400 μm ² for processing. In other embodiments, the size of the electronic component (the area of the attachment surface) is 1 μm ² to 2500 μm ² for processing.

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

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

In one embodiment, the above-mentioned processing method of the electronic component includes: arranging the electronic component on another sheet (for example, an adhesive sheet, a substrate, etc.) after the electronic component is peeled off. Example

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited by these examples. The evaluation methods in the examples are as follows. In addition, in the following evaluation, the adhesive sheet after peeling the separator was used. In addition, in the examples, as long as there is no clear description in particular, "parts" and "%" are based on weight.

之UV雷射光，以0.80 mW功率、40 kHz頻率進行脈衝掃描，而使氣體自氣體產生層產生。對於與脈衝掃描過之任意1點對應之黏著劑層表面，於雷射光照射結束1分鐘後，利用共聚聚焦雷射顯微鏡進行觀察，而測定垂直位移Y與水平位移X(直徑；半峰全幅值)。 於位移Y為8 μm以上之情形時，剝離性顯著優異(表中，◎)；於位移Y為0.6 μm以上且未達8 μm之情形時，剝離性良好(表中，〇)；於位移Y未達0.6 μm之情形時，剝離性不充分(表中，×)。 (9)黏著力(氣體產生層側) 於黏著片材之黏著劑層側貼合PET#25而獲得測定樣品。對於測定樣品之氣體產生層側相對於SUS430之黏著力，藉由依照JIS Z 0237：2000之方法(貼合條件：2 kg輥1個往返，拉伸速度：300 mm/min，剝離角度180°)進行測定。 (10)黏著力(黏著劑層) 於黏著片材之氣體產生層側貼合PET#25而獲得測定樣品。對於測定樣品之黏著劑層側相對於SUS430之黏著力，藉由依照JIS Z 0237：2000之方法(貼合條件：2 kg輥1個往返，拉伸速度：300 mm/min，剝離角度180°)進行測定。 (11)變形之面內均一性 以上述(8)之方式對氣體產生層照射UV雷射光。 利用顯微鏡對隨機選擇之2 mm×2 mm範圍之變形部進行觀察，於凸部之90個%以上為相同尺寸之情形時設為良(表中，〇)，於凸部之80個%以上且未達90個%為相同尺寸之情形時設為可(表中，△)，於凸部之未達80個%為相同尺寸之情形時設為差(表中，×)。所謂相同尺寸係指位移X之差在±20%以內。 (12)變形之位置選擇性 以上述(8)之方式對氣體產生層照射UV雷射光。 將僅雷射光照射部單獨變形之情形設為合格(〇)，將於雷射照射部周邊亦有複數處變形之情形設為不合格(×)。 (13)彈性模數 使用奈米壓痕儀(Hysitron Inc公司製造之Triboindenter TI-950)，藉由在特定溫度(25℃)之單一壓入法，於壓入速度約500 nm/sec、拔出速度約500 nm/sec、壓入深度約1500 nm之測定條件下測定氣體產生層截面之彈性模數。(1) When the transmittance is 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 SolidSpec3700", manufactured by Shimadzu Corporation), and let the incident light The incident is perpendicular to the gas barrier layer side of the sample, and the light transmittance in the wavelength region of 300 nm to 800 nm is measured. The transmittance at the wavelength of 360 nm of the selected transmittance spectrum. In the case of an adhesive sheet composed of only an adhesive layer, set it in a spectrophotometer while leaving the release liner on one side and measure it. After that, measure the transmission spectrum of the release liner alone. The transmission spectrum of the adhesive layer alone is obtained by subtraction. The transmittance at the wavelength of 360 nm of the selected transmittance spectrum. (2) Maximum gas generation peak temperature. Approximately 0.5 mg of the adhesive sheet sample is set in a furnace-type pyrolyzer, and the mass chromatogram is obtained by EGA-MS analysis of the components that are volatilized by heating. Using a furnace-type pyrolyzer (manufactured by Frontier Laboratories, trade name "PY2020iD") at a heating rate of 10°C/min from 40°C to 500°C, using GC/MS (Gas chromatography/mass spectrometry, gas chromatography/mass spectrometry) ) An analysis device (manufactured by JEOL, 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 initiation temperature The temperature of the adhesive sheet is raised by the same method as in (2) above, and the gas generation temperature rise calculated based on the EGA analysis is used as the vaporization initiation temperature. The gas generation rising temperature is defined as the temperature that reaches the half value of the maximum gas generation peak value of the EGA/MS chromatogram obtained by EGA analysis. (4) Gas generation species The adhesive sheet sample is set in an automatic sample combustion device (manufactured by Mitsubishi Chemical Analysis Technology Co., Ltd., trade name "AQF-2100H"), and the gas generated by heating at 400°C for 30 minutes is captured. By using ion chromatography to analyze the capture liquid, the gas species to be generated can be identified. (5) Use a differential thermal analysis device (manufactured by TA Instruments, trade name "Discovery TGA") at a temperature of 5% weight reduction, and set the flow rate to 25 ml/min under a _{10°C/min heating temperature and N 2 atmosphere.} The temperature at which the weight of the adhesive sheet is reduced by 5% is measured. (6) Use a differential thermal analysis device (manufactured by TA Instruments, trade name "Discovery TGA") at a temperature of 10% weight reduction, and set the flow rate to 25 ml/min under a _{heating temperature of 10°C/min and an N 2 atmosphere.} The temperature at which the weight of the adhesive sheet is reduced by 10% is measured. The 10% weight loss temperature was measured for the adhesive sheet and the gas generating layer (UV absorber). (7) The water vapor transmission rate is to cover the opening of the Al jig with the opening of 10 mm×10 mm to prepare the measurement sample, and set the measurement sample in the water vapor transmission measurement device (MOCON Manufactured by the company, the trade name "PERMATRAN-W3/34G") between the first chamber and the second chamber was evaluated by the MOCON measurement method. 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 for the adhesive sheet, adhesive layer, and intermediate layer. (8) The surface shape changes on the side of the gas generating layer of the adhesive sheet (the side opposite to the adhesive layer) and the laminated glass plate (manufactured by Matsuba Glass Co., Ltd., large glass slide S9112 (standard large white edging No. 2)) The measurement sample is obtained. From the side of the glass plate of the measurement sample, use a wavelength of 355 nm and a beam diameter of about 20 μm

The UV laser light is pulsed with 0.80 mW power and 40 kHz frequency to generate gas from the gas generating layer. For the surface of the adhesive layer corresponding to any point scanned by the pulse, one minute after the laser light is irradiated, observe it with a confocal laser microscope, 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 remarkably 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, ○); in the displacement When Y is less than 0.6 μm, the peelability is insufficient (in the table, ×). (9) Adhesive force (gas generation layer side) PET#25 was attached to the adhesive layer side of the adhesive sheet to obtain a measurement sample. For measuring the adhesive force of the gas generating layer side of the sample to SUS430, the method in accordance with JIS Z 0237: 2000 (fitting conditions: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180° ) Perform the measurement. (10) Adhesion (adhesive layer) PET#25 was attached to the gas generating layer side of the adhesive sheet to obtain a measurement sample. For measuring the adhesive force of the adhesive layer side of the sample with respect to SUS430, the method in accordance with JIS Z 0237: 2000 (fitting conditions: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180° ) Perform the measurement. (11) In-plane uniformity of deformation The gas generating layer is irradiated with UV laser light in the manner described in (8) above. Use a microscope to observe the deformed part randomly selected in the range of 2 mm×2 mm. When 90% or more of the convex part is the same size, it is set as good (in the table, ○), and 80% or more of the convex part And when less than 90% is the same size, it is set as OK (in the table, △), and when less than 80% of the convex part is the same size, it is set as the difference (in the table, ×). The so-called same size means that the difference of displacement X is within ±20%. (12) Selective position of deformation Irradiate the gas generating layer with UV laser light in the manner described in (8) above. The case where only the laser light irradiation part is deformed alone is regarded as pass (o), and the case where there are multiple deformations around the laser irradiation part is regarded as unacceptable (×). (13) The modulus of elasticity uses a nanoindenter (Triboindenter TI-950 manufactured by Hysitron Inc.), with a single indentation method at a specific temperature (25°C), at an indentation speed of about 500 nm/sec, Measure the elastic modulus of the cross section of the gas generating layer under the measuring conditions of an output speed of about 500 nm/sec and an indentation depth of about 1500 nm.

[Manufacturing Example 1] Preparation of adhesive a To toluene was added 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of ethyl acrylate, 4 parts by weight of 2-hydroxyethyl acrylate, 5 parts by weight of methyl methacrylate, and peroxide as a polymerization initiator After 0.2 parts by weight of benzoyl, it was heated to 70°C to obtain a toluene solution of acrylic copolymer (polymer A). A toluene solution of polymer A (polymer A: 100 parts by weight), 3 parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and a surfactant (manufactured by Kao, trade name) "EXCEPARL IPP") 5 parts by weight were mixed to prepare adhesive a. The composition of the adhesive a is shown in Table 1.

[Manufacturing 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, it was heated to 70°C to obtain an acrylic copolymer ( Polymer A2) in ethyl acetate. An ethyl acetate solution of polymer A2 (polymer A2: 100 parts by weight), 1 part by weight of epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), and isocyanate-based crosslinking agent (Manufactured by Nippon Polyurethane, trade name "Coronate L") 3 parts by weight were mixed to prepare adhesive b. The composition of the adhesive b is shown in Table 1.

[Manufacturing Example 3] Preparation of Adhesive I Adhesive I was prepared in the same manner as in Production Example 1, except that the blending amount of the crosslinking agent was 1 part by weight and the surfactant was not contained. The composition of the adhesive I is shown in Table 1.

[Manufacturing Example 3'] Preparation of adhesive c Except that the blending amount of the isocyanate-based crosslinking agent was set to 1 part by weight and the blending amount of the epoxy-based crosslinking agent was set to 0.4 parts by weight, an adhesive c was prepared in the same manner as in Production Example 2. The composition of the 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 Manufacturing example 3'Adhesive c Base polymer Material Acrylic Acrylic Acrylic Acrylic Polymer species Polymer A Polymer C Polymer A Polymer C Crosslinking agent Crosslinking agent 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) Crosslinking agent - Epoxy - Epoxy 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, 16 Comparative examples 4 to 5 Examples 17, 18

[Production Example 4] Preparation of composition a for forming an intermediate layer Add 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, and then heat to 70°C An ethyl acetate solution of acrylic copolymer (polymer B) was obtained. The ethyl acetate solution of polymer B (polymer B: 100 parts by weight), epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "Tetrad C") 1 part by weight, UV oligomer (Mitsubishi Chemical 50 parts by weight of the product manufactured by the company, brand name "Violet UV-1700B"), and 3 parts by weight of a photopolymerization initiator (manufactured by BASF Corporation, brand name "Omnirad 127") were mixed to prepare an intermediate layer forming composition a. Table 2 shows the composition of the composition a for forming an intermediate layer.

[Production Example 5] Preparation of composition b for forming an intermediate layer. Maleic acid modified styrene-ethylene-butylene-styrene block copolymer (SEBS: styrene part/ethylene-butene 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-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., Brand name "TETRAD-C") 3 parts by weight, fatty acid ester-based surfactant (manufactured by Kao Corporation, brand name "EXCEPARL IPP", molecular weight: 298.5, carbon number of alkyl group: 16) 3 parts by weight, and as a solvent The toluene was mixed to obtain the composition b for forming an intermediate layer. Table 2 shows the composition of the composition b for forming an intermediate layer.

[Table 2] Composition for forming intermediate layer Production Example 4 Composition a for forming an intermediate layer Production Example 5 Composition b for forming an intermediate layer Base polymer Material Acrylic SEBS series Polymer species Polymer B UV oligomer UV oligomer UV curable acrylic urethane - Product name, number of copies UV-1700B(50) - Crosslinking agent Crosslinking agent Epoxy Epoxy Product name, number of copies Tetrad C(1) Tetrad C(3) Photopolymerization initiator Photopolymerization initiator Benzophenone series - Product name, number of copies Irg127(3) - Example 2 Example 3

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

[Production Example 7] Preparation of composition b for forming a gas generating layer Except that the blending amount of the UV absorber was 10 parts by weight, the gas generating layer forming composition b was prepared in the same manner as in Production Example 5. Table 3 shows the composition of the composition b for forming a gas generating layer.

[Production Example 8] Preparation of composition c for forming a gas generating layer As the UV absorber, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris (commodity Except for the name "TINUVIN 460", manufactured by BASF Corporation) 10 parts by weight, in the same manner as in Manufacturing Example 5, a composition c for forming a gas generating layer was prepared. Table 3 shows the composition of the composition c for forming a gas generating layer.

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

[Production Example 10] Preparation of composition e for forming a gas generating layer As the UV absorber, 2-[5-chloro-2H-benzotriazol-2-yl]-4-methyl-6-(tertiary butyl)phenol (trade name "TINUVIN 326", manufactured by BASF) was used ) Except for 20 parts by weight, in the same manner as in Production Example 5, a composition e for forming a gas generating layer was prepared. Table 3 shows the composition of the composition e for forming a gas generating layer.

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

[Production Example 12] Preparation of composition g for forming a gas generating layer After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, it was heated to 70°C to obtain an acrylic copolymer ( Polymer C) in ethyl acetate solution. An ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 1 part by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and an ultraviolet absorber (manufactured by BASF, (Trade name "Tinuvin 477") 20 parts by weight were mixed to prepare a composition g for forming a gas generating layer. Table 3 shows the composition of the composition g for forming a gas generating layer.

[Production Example 13] Preparation of composition h for forming a gas generating layer After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, it was heated to 70°C to obtain an acrylic copolymer ( Polymer C) in ethyl acetate solution. The ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 0.1 parts by weight of epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD-C"), and ultraviolet absorber (BASF) Company manufactured, trade name "Tinuvin 477") 20 parts by weight were mixed to prepare a composition h for forming a gas generating layer. Table 3 shows the composition of the composition h for forming a gas generating layer.

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

[Production Example 15] Preparation of composition I for forming a gas generating layer The composition I for forming a gas generating layer was prepared in the same manner as in Production Example 5 except that the ultraviolet absorber was not prepared. Table 3 shows the composition of the composition I for forming a gas generating layer.

[Production Example 16] Preparation of composition I containing heat-expandable microspheres No ultraviolet absorber was prepared, the crosslinking agent was adjusted to 1.4 parts by weight, and 30 parts by weight of thermally expandable microspheres (manufactured by Matsumoto Oil and Fat Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere F-50D"), and terpene phenols Except for 10 parts by weight of an adhesion-imparting resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name "SUMILITERESIN PR51732"), a thermally expandable microsphere-containing composition I was prepared in the same manner as in Production Example 5.

[Production Example 17] Preparation of composition II containing thermally expandable microspheres In place of 10 parts by weight of terpene phenol-based adhesion-imparting resin (manufactured by Sumitomo Bakelite, brand name "SUMILITERESIN PR51732"), 20 parts by weight of terpene-phenol-based adhesion-imparting resin (manufactured by Yasuhara Chemical Company, brand name "YS POLYSTER T160") was used Except for this, a thermally expandable microsphere-containing composition II was prepared in the same manner as in Production Example 13.

[Production Example 14'] Preparation of composition j for forming a gas generating layer After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, it was heated to 70°C to obtain an acrylic copolymer ( Polymer C) in ethyl acetate solution. Ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 1 part by weight of isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane, trade name "Coronate L"), and epoxy-based crosslinking agent (Mitsubishi Gas 0.1 parts by weight of a chemical company, brand name "TETRAD-C") and 10 parts by weight of an ultraviolet absorber (manufactured by BASF company, brand name "TINUVIN 400") were mixed to prepare a composition j for forming a gas generating layer. Table 3 shows the composition of the composition j for forming a gas generating layer.

[Manufacturing Example 14''] Preparation of composition k for forming a gas generating layer Except that the blending amount of the UV absorber was 5 parts by weight, the gas generating layer forming composition k was prepared in the same manner as in Production Example 14. Table 3 shows the composition of the composition k for forming a gas generating layer.

[table 3] Composition for forming gas generating layer Production Example 6 Composition a for forming a gas generating layer Production Example 7 Composition b for forming a gas generating layer Production Example 8 Composition c for forming a gas generating layer Production Example 9 Composition d for forming a gas generating layer Production Example 10 Composition e for forming gas generating layer Base polymer Material Acrylic Acrylic Acrylic Acrylic Acrylic Polymer species Polymer A Polymer A Polymer A Polymer A Polymer A Crosslinking agent Crosslinking agent Isocyanate series Isocyanate series Isocyanate series Isocyanate series Isocyanate series Crosslinking agent parts Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) Coronate/L(1.5) UV absorber Types of UV absorbers (skeleton) Hydroxyphenyl tris series Hydroxyphenyl tris series Hydroxyphenyl tris series Hydroxyphenyl tris series 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 356 nm 356 nm 349 nm 336 nm 355 nm Remark Examples 1～4, 9～12 Example 5 Example 6 Example 7 Example 8 Composition for forming gas generating layer Production Example 11 Composition f for forming gas generating layer Production Example 12 Composition for forming a gas generating layer g Production Example 13 Composition h for forming a gas generating layer Production Example 14 Composition for forming gas generating layer i Production Example 14' Composition j for forming a gas generating layer Production Example 14'' Composition for forming a gas generating layer k Base polymer Material Acrylic Acrylic Acrylic SEBS series Acrylic Acrylic Polymer species Polymer B Polymer C Polymer C Polymer C Polymer C Crosslinking agent Crosslinking agent Isocyanate series Isocyanate series Epoxy Epoxy Isocyanate series Isocyanate series Crosslinking agent parts Coronate/L(1.0) Coronate/L(1.0) Tetrad C(0.1) Tetrad C(3) Coronate/L(1.0) Coronate/L(1.0) Crosslinking agent Isocyanate series Isocyanate series Epoxy Epoxy Epoxy Epoxy Crosslinking agent parts 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 Types of UV absorbers (skeleton) Hydroxyphenyl tris series Hydroxyphenyl tris series Hydroxyphenyl tris series Hydroxyphenyl tris series Hydroxyphenyl tris series Hydroxyphenyl tris series 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 356 nm 356 nm 356 nm 356 nm 336 nm 336 nm Remark Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Composition for forming gas generating layer Production Example 15 Composition I for forming a gas generating layer 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 Crosslinking agent Crosslinking agent Isocyanate series Isocyanate series Isocyanate series Crosslinking agent parts Coronate/L(1.5) Coronate/L(1.4) Coronate/L(1.4) UV absorber Types of UV absorbers (skeleton) - - - Product name, number of copies - - - Molecular weight of UV absorber - - - TGA10% weight reduction temperature [℃] - - - Maximum absorption wavelength of UV absorber - - - Remark 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 (thickness: 75 μm), followed by drying to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition a for forming a gas generating layer obtained in Production Example 6 was applied to a polyethylene terephthalate treated surface with a silicone release agent so that the thickness after the solvent volatilized (dried) became 7 μm A film (manufactured by Toray, trade name "Cerapeel", thickness: 38 μm), and then dried to form a gas generating layer precursor layer a on the polyethylene terephthalate film. The adhesive layer precursor layer a and the gas generating layer precursor layer a are laminated between rolls and bonded to obtain a film sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface Adhesive sheet (adhesive layer/gas generating layer). The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 2] The adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate treated surface with a silicone release agent in such a way that the thickness after the solvent volatilized (dried) became 15 μm The film (thickness: 75 μm) is then dried to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition a for forming an intermediate layer obtained in Production Example 4 was applied to a polyethylene terephthalate film with a silicone release agent treatment surface so that the thickness after solvent volatilization (drying) became 15 μm (Manufactured by Toray, trade name "Cerapeel" thickness: 38 μm), and then dried to form an intermediate precursor layer a on the polyethylene terephthalate film. Then, the adhesive layer precursor layer a and the intermediate layer precursor layer a were laminated between rolls to be bonded together, and UV irradiation was performed under the condition of ^{500 mJ/cm 2 from the intermediate layer precursor layer side to obtain a sandwiched belt} The laminate precursor layer a between the polyethylene terephthalate films on the silicone release agent treatment surface. The composition a for forming a gas generating layer obtained in Production Example 6 was applied to a polyethylene terephthalate treated surface with a silicone release agent so that the thickness after the solvent volatilized (dried) became 7 μm A film (manufactured by Toray, 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 intermediate layer precursor layer a side of the above-mentioned laminate precursor layer a, the intermediate layer precursor layer a of the laminate precursor layer a and The gas generating layer precursor layer a is laminated between rolls and bonded to obtain an adhesive sheet (adhesive layer/middle 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 (thickness: 75 μm), followed by drying to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition b for forming an intermediate layer obtained in Production Example 5 was applied to a polyethylene terephthalate film with a silicone release agent treatment surface so that the thickness after the solvent volatilized (dried) became 15 μm (Manufactured by Toray, trade name "Cerapeel" thickness: 38 μm), and then dried to form an intermediate precursor layer a on the polyethylene terephthalate film. Then, the adhesive layer precursor layer a and the intermediate layer precursor layer b are laminated between rolls to be laminated to obtain sandwiched between the polyethylene terephthalate film with the silicone release agent-treated surface The laminate precursor layer b. The composition a for forming a gas generating layer obtained in Production Example 6 was applied to a polyethylene terephthalate treated surface with a silicone release agent so that the thickness after the solvent volatilized (dried) became 7 μm A film (manufactured by Toray, 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 intermediate layer precursor layer b side of the above-mentioned laminated body precursor layer b, the intermediate layer precursor layer b of the laminated body precursor layer b and The gas generating layer precursor layer a is laminated between rolls and bonded to obtain an adhesive sheet (adhesive layer/middle 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 (thickness: 75 μm), followed by drying to form an adhesive layer precursor layer a on the polyethylene terephthalate film. The composition a for forming a gas generating layer obtained in Production Example 6 was applied to a polyethylene terephthalate treated surface with a silicone release agent so that the thickness after the solvent volatilized (dried) became 7 μm A film (manufactured by Toray, trade name "Cerapeel", thickness: 38 μm), and then dried to form a gas generating layer precursor layer a on the polyethylene terephthalate film. The adhesive layer precursor layer a was laminated between rolls and bonded to one side of a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror#2F51N" thickness: 2 μm). Then, the gas generating layer precursor layer a is laminated between rolls and bonded to the opposite side of the adhesive layer precursor layer a of the above-mentioned polyethylene terephthalate film. In this way, an adhesive sheet (adhesive layer/intermediate layer/gas generating layer) sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface was obtained. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 5] Except having used the composition b for gas generation layer formation instead of the composition a for gas generation layer formation, it carried out similarly to Example 4, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 6] Except having used the composition c for gas generation layer formation instead of the composition a for gas generation layer formation, it carried out similarly to Example 4, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 7] Except having used the composition d for gas generation layer formation instead of the composition a for gas generation layer formation, it carried out similarly to Example 4, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 4.

[Example 8] Except having used the composition e for gas generation layer formation instead of the composition a for gas generation layer formation, it carried out similarly to Example 4, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

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

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

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

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

[Example 13] Except having used the composition f for gas generation layer formation instead of the composition a for gas generation layer formation, it carried out similarly to Example 4, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 14] Except having used the composition g for gas generation layer formation instead of the composition a for gas generation layer formation, it carried out similarly to Example 4, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 5.

[Example 15] The composition h for forming a gas generating layer was applied to a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror S10",” thickness: 50 μm) on one side, and a gas generating layer is formed. Then, the adhesive b was applied to a polyethylene terephthalate film (manufactured by Toray Co., Ltd., trade name "Cerapeel" thickness: 38 μm), and an adhesive layer is formed. Then, the gas generating layer and the adhesive 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 treatment surface ). The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Example 16] Except having used the composition i for gas generation layer formation instead of the composition h for gas generation layer formation, it carried out similarly to Example 15, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Example 17] The composition j for forming a gas generating layer was applied to a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror S10",” thickness: 50 μm) on one side, and a gas generating layer is formed. Then, the adhesive a was applied to a polyethylene terephthalate film (manufactured by Toray Co., Ltd., trade name "Cerapeel" thickness: 38 μm), and an adhesive layer is formed. Then, the gas generating layer and the adhesive 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 treatment surface ). The obtained adhesive sheet was used for the above evaluation. The results are shown in Table 6.

[Example 18] Except having used the composition k for gas generation layer formation instead of the composition j for gas generation layer formation, it carried out similarly to Example 17, and obtained the adhesive sheet. 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 the adhesive layer [g/(m ²・day)] 3435.3 4059.3 4059.3 4059.3 4059.3 4059.3 4059.3 middle layer Intermediate layer material - Composition for forming intermediate layer a Composition for forming intermediate layer 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 for forming gas generating layer a Composition for forming gas generating layer a Composition for forming gas generating layer a Composition for forming gas generating layer a Composition b for forming gas generating layer Composition for forming gas generating layer 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 356 nm 356 nm 356 nm 356 nm 356 nm 349 nm 336 nm 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 Log (Er (gas) × 10 6) ≧ 8.01 × h (gas) - under the elastic modulus of the layer of gas calculated value ^0.116 [MPa] 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 of the elastic modulus of the gas generating layer calculated according to Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^{-0.092 [MPa]} 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 of the elastic modulus of the gas generating layer calculated according to 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 of the elastic modulus of the gas generating layer calculated according to 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 start 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 characteristics Water vapor transmission rate [g/(m ²・day)] 3,158.9 1238.1 198.1 334.2 330.2 328.4 339.4 Surface shape change 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 state Foam convex Foam convex Foam convex Foam convex Foam convex Foam convex Foam convex Adhesive force relative to SUS430 [N/20 mm] (adhesive layer side) 4.20 3.46 2.32 0.33 0.31 0.35 0.39 Adhesion to SUS430 [N/20 mm] (side of gas generating layer) 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 the adhesive layer [g/(m ²・day)] 4059.3 6216.2 6216.2 4,369.7 3,754.3 4059.3 4059.3 middle layer Intermediate 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 for forming gas generating layer a Composition for forming gas generating layer a Composition for forming gas generating layer a Composition for forming gas generating layer a Composition f for forming gas generating layer Composition for forming gas generating layer g 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 355 nm 356 nm 356 nm 356 nm 356 nm 356 nm 356 nm 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 Log (Er (gas) × 10 6) ≧ 8.01 × h (gas) - under the elastic modulus of the layer of gas calculated value ^0.116 [MPa] 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 of the elastic modulus of the gas generating layer calculated according to Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^{-0.092 [MPa]} 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 of the elastic modulus of the gas generating layer calculated according to 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 of the elastic modulus of the gas generating layer calculated according to 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 start 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 characteristics Water vapor transmission rate [g/(m ²・day)] 298.6 280.8 252.3 314.7 346.0 336.2 284.1 Surface shape change 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 state Foam convex Foam convex Foam convex Foam convex Foam convex Foam convex Foam convex Adhesive force relative to SUS430 [N/20 mm] (adhesive layer side) 1.05 0.21 0.19 0.32 0.46 0.46 0.42 Adhesion to SUS430 [N/20 mm] (side of gas generating layer) 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 the adhesive layer [g/(m ²・day)] 3,754.3 3,754.3 4,369.7 4,369.7 middle layer Intermediate 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 Composition h for forming gas generating layer Composition for forming gas generating layer i Composition j for forming gas generating layer Composition for forming gas generating layer 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 356 nm 356 nm 336 nm 336 nm 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 Log (Er (gas) × 10 6) ≧ 8.01 × h (gas) - under the elastic modulus of the layer of gas calculated value ^0.116 [MPa] 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 of the elastic modulus of the gas generating layer calculated according to Log(Er(gas)×10 ⁶ )≧7.66×h(gas) ^{-0.092 [MPa]} 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 of the elastic modulus of the gas generating layer calculated according to 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 of the elastic modulus of the gas generating layer calculated according to Log(Er(gas)×10 ⁶ )≦47.675×h(gas) ^{-0.519 [MPa]} 11,765.71 11,765.71 11,765.71 11,765.71 Substrate 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 start 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 characteristics Water vapor transmission rate [g/(m ²・day)] 9.2 10.1 9.8 11.1 Surface shape change Height (Y: vertical displacement) 1.8 4.3 0.7 0.6 Diameter (X: horizontal displacement) 18.3 20.5 12.1 9.8 state Foam convex Foam convex Foam convex Foam convex Adhesive force relative 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] Except having used the composition I for gas generation layer formation instead of the composition a for gas generation layer formation, it carried out similarly to Example 4, and obtained the adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (12). The results are shown in Table 7.

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

[Comparative Example 3] Use adhesive I instead of adhesive a, set the thickness of the adhesive layer to 10 μm, use a PET film with a thickness of 100 μm as the intermediate layer, and use a combination containing heat-expandable microspheres instead of the gas generating layer forming composition a Except that the substance II formed a 48 μm gas generating layer, an adhesive sheet was obtained in the same manner as in Example 4. 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 the adhesive layer [g/(m ²・day)] 4059.3 - - middle layer Intermediate layer material PET PET PET Thickness [μm] 2 188 100 Water vapor transmission rate of the middle layer [g/(m ²・day)] 3450 - - Gas generating layer Gas generating layer material Composition I for forming gas generating layer Composition containing heat-expandable microspheres I Composition containing heat-expandable microspheres II 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 start temperature [℃] 350 (from polymer) - - Gas species hydrocarbon hydrocarbon hydrocarbon TGA5% weight reduction temperature [℃] 336.519 - - TGA10% weight reduction temperature [℃] 362.492 - - Gas barrier characteristics Water vapor transmission rate [g/(m ²・day)] 260.1 - - Surface shape change Height (Y: vertical displacement) - ≧100 μm ≧100 μm Diameter (X: horizontal displacement) - ≧200 μm ≧200 μm state Crack × Plural foam convex Plural foam convex Adhesive force relative to SUS430 [N/20 mm] (adhesive layer side) 2.12 - - Adhesion to SUS430 [N/20 mm] (side of gas generating layer) 4.60 - - Peelability X ◎ ◎ In-plane uniformity of deformation - X X Location selectivity 〇 X X

4: sample 5A, 5B: Specimen 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 an 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 explaining the method of measuring the puncture strength.

10: Gas generation layer

20: Adhesive layer

100: Adhesive sheet

Claims (17)

An adhesive sheet is provided with a gas generating layer and at least one adhesive layer arranged 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 adhesive sheet of claim 1, wherein the gas generating layer is a layer that can absorb ultraviolet rays. The adhesive sheet of claim 2, wherein the gas generating layer contains an ultraviolet absorber. The adhesive sheet according to any one of claims 1 to 3, wherein the thickness of the gas generating layer is 0.1 μm-50 μm. The adhesive sheet according to any one of claims 1 to 4, wherein the gas generating layer is a layer that generates hydrocarbon-based gas. The adhesive sheet according to any one of claims 1 to 5, wherein the gasification initiation temperature of the gas generating layer is 150°C to 500°C. Such as the adhesive sheet of any one of claims 1 to 6, wherein the elastic modulus Er(gas) [unit: MPa] and thickness h(gas) [unit: μm] satisfies the following formula (1): Log(Er(gas)×10 ⁶ )≧8.01×h(gas) ^-0.116··· (1). The adhesive sheet according to any one of claims 1 to 7, wherein the thickness of the adhesive layer is 0.1 μm-50 μm. The adhesive sheet of any one of claims 1 to 8, wherein the amount of deformation of the surface of the adhesive layer generated by irradiating the adhesive sheet with laser light is 0.6 μm or more in terms of the vertical displacement of the adhesive layer . Such as the adhesive sheet of any one of Claims 1 to 9, the transmittance of ultraviolet rays with a wavelength of 360 nm is 30% or less. For the adhesive sheet of any one of claims 1 to 10, the 10% weight reduction temperature is 200°C to 500°C. For example, the adhesive sheet of any one of claims 1 to 11 has a water vapor transmission rate of 5000 g/(m ² ·day) or less. A processing method of electronic parts, comprising: attaching the electronic parts to the adhesive sheet of any one of claims 1 to 12; and irradiating the adhesive sheet with laser light to peel off the electronic from the adhesive sheet Component. Such as claim 13 for the processing method of electronic components, wherein the above-mentioned peeling of the electronic components is performed at selected locations. For example, the processing method of electronic components in claim 13 or 14, which includes: After attaching the electronic component to the adhesive sheet and before peeling the electronic component from the adhesive sheet, Perform specific processing on the electronic part. Such as the processing method of electronic parts in claim 15, wherein the above-mentioned processing is grinding processing, cutting processing, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer, arrangement, Repair or device surface protection. For example, the method for processing an electronic component according to any one of claims 13 to 16, which includes: arranging the electronic component on another sheet after peeling the electronic component from the adhesive sheet.

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