WO2021124854A1 - Adhesive sheet - Google Patents

Abstract

Provided is an adhesive sheet that can be, in a preferable manner, temporarily fixed to a small electronic component (for example, a chip having a size of 100 square-µm or less), and can be satisfactorily detached.　The adhesive sheet according to the present invention is provided with a gas generation layer and at least one adhesive agent layer disposed on one side of the gas generation layer. The adhesive agent layer is a layer that deforms when the adhesive sheet is irradiated with laser light. In one embodiment, the gas generation layer is a layer capable of absorbing ultraviolet rays.

Description

Adhesive sheet

The present invention relates to an adhesive sheet.

Conventionally, when processing (processing) an electronic component, an operation of temporarily fixing the object to be processed on the adhesive sheet at the time of processing and peeling the object to be processed from the adhesive sheet after the processing may be performed. is there. As the pressure-sensitive adhesive sheet used for such an operation, a pressure-sensitive adhesive sheet which has a predetermined adhesive strength at the time of treatment and whose adhesive strength can be reduced after the treatment may be used. As one of such pressure-sensitive adhesive sheets, a pressure-sensitive adhesive sheet having a heat-expandable microsphere contained in the pressure-sensitive adhesive layer has been proposed (for example, Patent Document 1). The adhesive sheet containing the heat-expandable microspheres has a predetermined adhesive strength, but the heat-expandable microspheres are expanded by heating to form irregularities on the adhesive surface to reduce the contact area. It is characterized by a decrease or disappearance of force. Such an adhesive sheet has an advantage that the object to be treated can be easily peeled off without external stress.

However, in recent years, along with the trend toward weight reduction and an increase in the number of mounted devices, the miniaturization of electronic components has progressed, and it is necessary to temporarily fix electronic components that have been miniaturized to the same size as the above-mentioned heat-expandable microspheres. Sex is occurring. When temporarily fixing and processing electronic components that have been miniaturized, the influence of the presence of thermally expandable microspheres with a large particle size, the absence of thermally expandable microspheres, etc. due to the variation in particle size, etc. It becomes large, and good peeling may not be possible at the relevant portion.

Japanese Unexamined Patent Publication No. 2001-131507

The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to satisfactorily temporarily fix a small electronic component (for example, a chip having a size of 100 μm □ or less) and to peel it off satisfactorily. The purpose is to provide an adhesive sheet that can be used.

The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet including a gas generating layer and at least one pressure-sensitive adhesive layer arranged on one side of the gas-generating layer, and the pressure-sensitive adhesive layer is a laser to the pressure-sensitive adhesive sheet. A layer whose surface is deformed by light irradiation.
In one embodiment, the gas generating layer is a layer capable of absorbing ultraviolet rays.
In one embodiment, the gas generating layer comprises an ultraviolet absorber.
In one embodiment, the thickness of the gas generating layer is 0.1 μm to 50 μm.
In one embodiment, the gas generating layer is a layer that generates a hydrocarbon gas.
In one embodiment, the gasification start temperature of the gas generation 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 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 pressure-sensitive adhesive layer is 0.1 μm to 50 μm.
In one embodiment, the amount of deformation of the surface of the pressure-sensitive adhesive layer due to laser irradiation of the pressure-sensitive adhesive sheet is 0.6 μm or more in the vertical displacement of the pressure-sensitive adhesive layer.
In one embodiment, the pressure-sensitive adhesive sheet has an ultraviolet transmittance of 30% or less at a wavelength of 360 nm.
In one embodiment, the pressure-sensitive adhesive sheet has a 10% weight loss temperature of 200 ° C. to 500 ° C.
In one embodiment, the pressure-sensitive adhesive sheet has a water vapor permeability of 5000 g / (m ² · day) or less.
According to another aspect of the present invention, there is provided a method of processing electronic components. The method for processing the electronic component includes sticking the electronic component on the pressure-sensitive adhesive sheet and irradiating the pressure-sensitive adhesive sheet with laser light to peel off the electronic component from the pressure-sensitive adhesive sheet.
In one embodiment, the electronic components are peeled off in a regioselective manner.
One embodiment includes attaching the electronic component to the pressure-sensitive adhesive sheet and then performing a predetermined treatment on the electronic component before peeling the electronic component from the pressure-sensitive adhesive sheet.
In one embodiment, the process is grinding, dicing, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, inspection, cleaning, transfer, alignment, repair or device surface protection. ..
In one embodiment, the method of processing the electronic component comprises peeling the electronic component from the pressure-sensitive adhesive sheet and then arranging the electronic component on another sheet.

According to the present invention, it is possible to provide an adhesive sheet capable of satisfactorily temporarily fixing a small electronic component (for example, a chip having a size of 100 μm □ or less) and satisfactorily peeling it off.

It is the schematic sectional drawing of the pressure-sensitive adhesive sheet by one Embodiment of this invention. It is schematic sectional drawing of the pressure-sensitive adhesive sheet by another embodiment of this invention. It is the schematic explaining the measuring method of the piercing strength.

A. Overview Figure 1 of the adhesive sheet is a schematic sectional view of a pressure-sensitive adhesive sheet according to a preferred embodiment of the present invention. The pressure-sensitive adhesive sheet 100 includes a gas generation layer 10 and at least one pressure-sensitive adhesive layer 20 arranged on one side of the gas generation layer 10. The gas generation layer 10 generates gas by irradiation with laser light. More specifically, the gas generation layer 10 is a layer that generates gas by gasifying its components by laser light irradiation. The surface of the pressure-sensitive adhesive layer 20 can be deformed by irradiating the pressure-sensitive adhesive sheet (substantially the gas generating layer) with laser light. In one embodiment, the deformation is due to the gas generated from the gas generating layer 10 and can occur on the opposite side of the pressure-sensitive adhesive layer 20 from the gas generating layer 10. As the laser light, UV laser light is typically used.

The pressure-sensitive adhesive sheet of the present invention can be used by attaching an object to be treated such as an electronic component to the pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet of the present invention includes a gas generating layer, and partially generates gas in a minute range by laser light irradiation. As described above, the pressure-sensitive adhesive layer is deformed due to the generation of the gas, and as a result, peelability is exhibited in the portion irradiated with the laser beam. Typically, the laser beam is emitted from the side opposite to the pressure-sensitive adhesive layer of the gas generating layer. According to the present invention, since deformation can be generated in a minute range as described above, the small electronic component can be satisfactorily peeled off even when processing (processing) an extremely fine small electronic component. Can be done. Even when a small electronic component that requires peeling and a small electronic component that does not require peeling are temporarily fixed next to each other, they should be peeled at the part to be peeled and not peeled at the part not to be peeled. That is, only the small electronic component that needs to be peeled can be peeled off, and unnecessary detachment of the small electronic component can be prevented. In order to satisfactorily deform the pressure-sensitive adhesive layer, it is preferable that at least a part of the generated gas is barriered so as not to come out of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive layer can function as a gas barrier layer. In addition, the pressure-sensitive adhesive sheet has excellent directivity at the time of peeling, can be peeled only at a desired location, is prevented from being damaged, and has an advantage in that there is little adhesive residue. The directivity at the time of peeling is an index showing the position accuracy when the adherend such as a small electronic component is peeled from the adhesive sheet and ejected aiming at a place separated by a certain distance. If the directivity is excellent, it is possible to prevent the adherend from flying in an unexpected direction at the time of peeling.

Deformation of the pressure-sensitive adhesive layer means displacement that occurs in the normal direction (thickness direction) and the horizontal direction (direction orthogonal to the thickness direction) of the pressure-sensitive adhesive layer. The deformation of the pressure-sensitive adhesive layer is caused by, for example, generating gas from the gas generating layer by pulse scanning at 0.80 mW output and frequency 40 kHz using UV laser light having a wavelength of 355 nm and a beam diameter of about 20 μmφ. The deformed shape is observed, for example, by measuring any one spot pulse-scanned one minute after laser light irradiation with a confocal laser scanning microscope or a non-contact interference microscope (WYKO). The shape may be foam (convex), through hole (concavo-convex), or concave (concave), and these deformations can cause peelability. In order to efficiently peel off electronic components in the normal direction, it is preferable that the displacement change in the normal direction before and after laser light irradiation is large, and in particular, those having a foamed shape are suitable. Foaming (convex) is defined as the vertical displacement Y at the highest point and the horizontal displacement X (diameter) at the full width at half maximum with reference to the surface of the adhesive sheet in the unirradiated portion. For through holes (concavities and convexities) and dents (concave) that form holes after laser light irradiation, the difference between the highest point and the lowest point is defined as the vertical displacement Y, and the diameter of the hole is defined as the horizontal displacement X. Hereinafter, the portion deformed by laser light irradiation is also referred to as a “deformed portion”. The vertical displacement of the pressure-sensitive adhesive layer is preferably 0.6 μm or more, more preferably 0.7 μm or more, and further preferably 1.0 μm or more. Within such a range, the peelability is excellent and the directivity at the time of peeling is excellent. In addition, it can be peeled off in a desired direction with high accuracy, and as a result, adhesive 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 pressure-sensitive adhesive layer is preferably 80 μm or less, more preferably 50 μm or less, and further preferably 40 μm or less. Within such a range, it is possible to preferably peel off the small adherend only at a desired location. Further, the same effect can be expected when the adherends are arranged at narrow intervals. The lower limit of the horizontal displacement is, for example, 3 μm (preferably 4 μm).

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

Although not shown, the adhesive sheet may further include other layers. For example, a base material, another pressure-sensitive adhesive layer, or the like may be provided on the surface of the gas generating layer opposite to the pressure-sensitive adhesive layer. As the base material, for example, a film formed from any suitable resin is used.

The adhesive strength of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention to SUS430 is preferably 0.1 N / 20 mm or more, more preferably 0.2 N / 20 mm to 50 N / 20 mm, and further preferably 0.5 N / 20 mm. It is ~ 40N / 20mm, particularly preferably 0.7N / 20mm to 20N / 20mm, and most preferably 1N / 20mm to 10N / 20mm. Within such a range, for example, an adhesive sheet exhibiting good adhesiveness can be obtained as a temporary fixing sheet used for manufacturing electronic parts. In the present specification, the adhesive strength is measured in an environment of 23 ° C. by a method according to JIS Z 0237: 2000 (bonding conditions: 2 kg roller 1 reciprocation, tensile speed: 300 mm / min, peeling angle 180 °). Adhesive strength.

In one embodiment, the gas generating layer has a predetermined adhesive force. The adhesive strength of the gas generating layer of the pressure-sensitive adhesive sheet of the present invention to SUS430 is preferably 0.1 N / 20 mm or more, more preferably 0.5 N / 20 mm to 50 N / 20 mm, and further preferably 1 N / 20 mm to 40 N. / 20 mm, particularly preferably 1.5N / 20mm to 30N / 20mm, and most preferably 2N / 20mm to 20N / 20mm. Within such a range, for example, an adhesive sheet exhibiting good adhesiveness can be obtained as a temporary fixing sheet used for manufacturing electronic parts.

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

The haze value of the pressure-sensitive adhesive sheet of the present invention is preferably 50% or less, more preferably 0.1% to 40%, and further preferably 0.5% to 30%. Within such a range, the adherend (for example, a base for temporarily fixing the electronic component) can be visually recognized through the adhesive sheet, and for example, the fixing base is used to indicate the temporary fixing position of the electronic component. It is possible to obtain an adhesive sheet having excellent visibility of the markings provided on the above. Since the pressure-sensitive adhesive sheet of the present invention can be constructed without including an insoluble filler in each layer of the pressure-sensitive adhesive sheet, it is possible to obtain a pressure-sensitive adhesive sheet having a small haze value and excellent visibility of an adherend as described above. it can. Such an effect is an excellent effect that cannot be obtained with an adhesive sheet containing an insoluble filler (for example, heat-expandable microspheres).

Water vapor permeability of the pressure-sensitive adhesive sheet of the present invention is preferably not 5000g ^/ (m 2 · day) or less, more preferably 4800g ^/ (m 2 · day) or less, more preferably 4500g ^/ (m 2 · day ) Or less, more preferably 4200 g / (m ² · day) or less. In the pressure-sensitive adhesive sheet having a water vapor transmittance in such a range, gas escape caused by laser light irradiation is prevented, and a deformed portion having an excellent shape is formed in the pressure-sensitive adhesive layer. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy. The smaller the water vapor permeability of the pressure-sensitive adhesive sheet of the present invention is, the more preferable it is, but the lower limit thereof is, for example, 0.1 g / (m ² · day). The water vapor permeability can be measured by a measuring method based on JIS K7129B in an atmosphere of 30 ° C. and 90% RH.

Water vapor permeability of the laminate of the adhesive layer and the intermediate layer is preferably not 10000g ^/ (m 2 · day) or less, more preferably 7000g ^/ (m 2 · day) or less, more preferably 5000g / ^(m 2 · day) or less, further preferably 4800 g ^/ (m 2 · day) or less, more preferably not more 4500 g ^/ (m 2 · day) or less, particularly preferably 4200g / ^{(m 2} · day) or less. Within such a range, the laminate composed of the pressure-sensitive adhesive layer and the intermediate layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed in the pressure-sensitive adhesive layer. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy. Water vapor permeability of laminate comprising a pressure-sensitive adhesive layer and the intermediate layer is preferably as small, its lower limit is, for example, ^{1g / (m 2 · day)} .

The piercing strength of the laminate composed of the pressure-sensitive adhesive layer and the intermediate layer is preferably 10 mN to 5000 mN, more preferably 30 mN to 4000 mN, further preferably 50 mN to 3000 mN, and particularly preferably 100 mN to 2000 mN. .. Within such a range, the laminate composed of the pressure-sensitive adhesive layer and the intermediate layer functions well as a gas barrier layer, and the shape change is preferably caused by gas generation. As a result, the shape of the pressure-sensitive adhesive layer is deformed excellently. The part is formed. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy. As shown in FIG. 3, the piercing strength was measured by using a compression tester 6 (manufactured by Kato Tech Co., Ltd., trade name “KES-G5”) in sample holders 5A and 5B having a circular opening with a diameter of 11.28 mm. 4 (for example, a laminated body) is held and measured. More specifically, at a measurement temperature of 23 ° C., a piercing needle (radius of curvature: 1 mm) is pierced into the sample (piercing speed: 0.1 mm / s) at the center of the circular opening of the circular opening at the fracture point. The maximum load can be the piercing strength.

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

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

The 10% weight loss temperature of the pressure-sensitive adhesive sheet is preferably 200 ° C. to 500 ° C., more preferably 220 ° C. to 450 ° C., further preferably 250 ° C. to 400 ° C., and particularly preferably 270 ° C. to 370 ° C. ℃. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation. The 10% weight loss temperature of the pressure-sensitive adhesive sheet was reduced by 10% by weight with respect to the weight before the temperature rise in the TGA analysis when the temperature of the pressure-sensitive adhesive sheet was raised (that is, the weight of the pressure-sensitive adhesive sheet was reduced with respect to the weight before irradiation. It means the temperature at the time (which became 90%).

B. Gas generating layer The gas generating layer can be a layer capable of absorbing ultraviolet rays. In one embodiment, the gas generating layer comprises a UV absorber. By containing the ultraviolet absorber, it is possible to form a gas generating layer capable of absorbing laser light and gasifying it. Typically, the gas generating layer contains an ultraviolet absorber and an adhesive A. Preferably, the UV absorber is present dissolved in the pressure-sensitive adhesive A. If the ultraviolet absorber is dissolved in the pressure-sensitive adhesive A and exists, a deformed portion (for example, an uneven portion) can be generated at any portion of the pressure-sensitive adhesive layer, and the deformed portion (for example, the uneven portion) can be generated. It is possible to obtain an adhesive sheet with little variation in the shape of. By using such an adhesive sheet, a deformed portion (for example, an uneven portion) can be generated at a desired portion with high accuracy, and the effect of the present invention becomes remarkable. In the present specification, the state of "dissolved in the pressure-sensitive adhesive" means that the ultraviolet absorber does not exist as particles in the gas generating layer. More specifically, it is preferable that the gas generating layer does not contain an ultraviolet absorber having a particle diameter of 10 μm or more in the particle distribution measurement in the cross section of the gas generating layer by X-ray CT. The gas generating layer may or may not contain an insoluble component in the pressure-sensitive adhesive. In one embodiment, the presence / absence and content of the insoluble component in the gas generating layer is evaluated by the haze value of the gas generating layer, and the smaller the haze value, the smaller the content of the insoluble component in the gas generating layer. Be evaluated. Preferably, the gas generating layer is substantially free of adhesive-insoluble components.

The elastic modulus of the cross section of the gas generating layer by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. Within such a range, the shape of the gas generating layer is preferably changed due to gas generation, and as a result, a deformed portion having an excellent shape is formed in the pressure-sensitive adhesive layer. The elastic modulus by the nanoindentation method is obtained by continuously measuring the load on the indenter and the pressing depth when the indenter is pushed into the sample (for example, the adhesive surface) during loading and unloading. Load load-The elastic modulus obtained from the indentation depth curve. The elastic modulus by the nanoindentation method is the displacement-load hysteresis curve obtained by pressing a diamond Berkovich type (triangular pyramid type) probe perpendicularly to the cut section of the measurement target layer, and the software attached to the measuring device. It is obtained by numerical processing with (triboscan). In the present specification, the elastic modulus of the cross section by the nanoindentation method refers to the elastic modulus of the cross section by a single indentation method at a predetermined temperature (25 ° C.) using a nanoindenter (Titanium Inc. Triboinder TI-950). The elastic modulus measured under the measurement conditions of 500 nm / sec, a pull-out speed of about 500 nm / sec, and a pushing depth of about 1500 nm. The elastic modulus of the gas generating layer can be adjusted by the type of material contained in the corresponding layer, the structure of the base polymer constituting the material, the type and amount of the additive added to the corresponding layer, and the like. .. In the present specification, the elastic modulus by the nanoindentation method does not mean the cross section or the surface, and the elastic modulus means the elastic modulus by the nanoindentation method of the cross section.

The elastic modulus of the surface of the gas generating layer by the nanoindentation method is preferably 0.01 MPa to 1000 MPa, more preferably 0.05 MPa to 800 MPa. Within such a range, the shape of the gas generating layer is preferably changed due to gas generation, and as a result, a deformed portion having an excellent shape is formed in the pressure-sensitive adhesive layer. The elastic modulus by the nanoindentation method is obtained by continuously measuring the load on the indenter and the pressing depth when the indenter is pushed into the sample (for example, the adhesive surface) during loading and unloading. Load load-The elastic modulus obtained from the indentation depth curve. The elastic modulus by the nanoindentation method is the displacement-load hysteresis curve obtained by pressing a diamond Berkovich type (triangular pyramid type) probe vertically against the measurement target layer, using the software (triboscan) attached to the measuring device. Obtained by numerical processing. In the present specification, the elastic modulus of the surface by the nanoindentation method refers to the elastic modulus of the surface by a single indentation method at a predetermined temperature (25 ° C.) using a nanoindenter (Titanium Inc. Triboinder TI-950). The elastic modulus was measured under the measurement conditions of 500 nm / sec, a pull-out speed of about 500 nm / sec, and a pushing depth of about 3000 nm. The elastic modulus of the gas generating layer can be adjusted by the type of material contained in the corresponding layer, the structure of the base polymer constituting the material, the type and amount of the additive added to the corresponding layer, and the like. .. In the present invention, there is a significant difference between the elastic modulus by the nanoindentation method measured by the above method with the cross section as the measurement surface and the elastic modulus by the nanoindentation method measured by the above method with the surface as the measurement surface. If it is difficult to measure from the cross section, the value measured from the surface can be adopted as the measured value from the cross section.

The gasification start temperature of the gas generation layer is preferably 150 ° C. to 500 ° C., more preferably 170 ° C. to 450 ° C., further preferably 190 ° C. to 420 ° C., and particularly preferably 200 ° C. to 400 ° C. ℃. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation. In the present specification, the gasification start temperature of the gas generation layer means the gas generation rise temperature calculated from the EGA analysis when the temperature of the pressure-sensitive adhesive sheet is raised. The gas generation rise temperature is defined as the temperature at which half of the maximum gas generation peak in the EGA / MS spectrum obtained from EGA analysis is reached. The lower the gasification start temperature, the lower the temperature at which gas begins to be generated when the laser beam is irradiated, and a sufficient amount of gas is generated even when the laser beam is irradiated with a smaller output. In one embodiment, the gasification start temperature of the gas generating layer corresponds to the gasification start temperature of the ultraviolet absorber.

The 10% weight loss temperature of the gas generating layer is preferably 150 ° C. to 500 ° C., more preferably 170 ° C. to 450 ° C., and further preferably 200 ° C. to 400 ° C. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation. The 10% weight reduction temperature of the gas generation layer means that the weight of the gas generation layer is the weight before the temperature rise in the TGA analysis when the temperature of the pressure-sensitive adhesive sheet is raised (for example, when the temperature is raised by laser light irradiation). It means the temperature at the time when the weight of the gas generating layer 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 to 50 μm, more preferably 1 μm to 40 μm, further preferably 2 μm to 30 μm, and particularly preferably 5 μm to 20 μm. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.

The elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] of the gas generating layer 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, since the gas generating layer is configured to satisfy the above formula (1), excessive deformation due to the gas generated from the gas generating layer is prevented, and the adhesive sheet is satisfactorily formed by laser light irradiation. Deform. By forming such a gas generating layer, it is possible to cause surface deformation in a minute range without arranging a thick barrier layer (adhesive layer) as a layer for preventing excessive deformation, and the pressure-sensitive adhesive. The layer (gas barrier layer) can be flexibly configured.

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

In one embodiment, the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] by the nanoindentation method further satisfy the following formula (4).
Log (Er (gas) x 10 ⁶ ) ≤ 47.675 x 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. Is less than 5%. The lower limit of the ultraviolet transmittance of the gas generating layer at a wavelength of 360 nm is, for example, 0% (preferably 0.05%, more preferably 0.1%).

The haze value of the gas generating layer is preferably 55% or less, more preferably 0.1% to 50%, and further preferably 0.5% to 40%.

B-1. Ultraviolet absorber As the ultraviolet absorber, any suitable ultraviolet absorber can be used as long as the effects of the present invention can be obtained. Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a salicylate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like. Of these, a triazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber is preferable, and a triazine-based ultraviolet absorber is particularly preferable. In particular, when an acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive A, a triazine-based ultraviolet absorber can be preferably used because the acrylic pressure-sensitive adhesive has high compatibility with the base polymer. The triazine-based ultraviolet absorber is more preferably composed of a compound having a hydroxyl group, and particularly preferably an ultraviolet absorber composed of a hydroxyphenyltriazine-based compound (hydroxyphenyltriazine-based ultraviolet absorber).

Examples of the hydroxyphenyltriazine-based ultraviolet absorber include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hydroxyphenyl and [(C10). -C16 (mainly C12-C13) alkyloxy) methyl] Reaction product with oxylane (trade name "TINUVIN 400", manufactured by BASF), 2- [4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4) Reaction product of -dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate (trade name "TINUVIN 405", manufactured by BASF), 2,4-bis (2-hydroxy-4) -Butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine (trade name "TINUVIN 460", manufactured by BASF), 2- (4,6-diphenyl-1,3) 5-Triazine-2-yl) -5-[(hexyl) oxy] -phenol (trade name "TINUVIN 1577", manufactured by BASF), 2- (4,6-diphenyl-1,3,5-triazine-2) -Il) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol (trade name "Adecastab LA-46", manufactured by ADEKA Co., Ltd.), 2- (2-Hydroxy-4- [1-] Octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (trade name "TINUVIN 479", manufactured by BASF), trade name "TINUVIN 477" manufactured by BASF And so on.

Examples of the benzotriazole-based ultraviolet absorber (benzotriazole-based compound) include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (trade name "TINUVIN PS", manufactured by BASF) and benzene. Ester compounds of propanoic acid and 3- (2H-benzotriazole-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) (trade name "TINUVIN 384") -2 ", manufactured by BASF), Octyl 3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [ 3-tert-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2yl) phenyl] propionate mixture (trade name "TINUVIN 109", manufactured by BASF), 2- (2H-benzotriazole) -2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name "TINUVIN 900", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -6- (1-Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name "TINUVIN 928", manufactured by BASF), methyl 3- (3- (2H-benzotriazole) -2-Il) -5-tert-Butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (trade name "TINUVIN 1130", manufactured by BASF), 2- (2H-benzotriazole-2-yl) ) -P-Cresol (trade name "TINUVIN P", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name) "TINUVIN 234", manufactured by BASF), 2- [5-chloro-2H-benzotriazole-2-yl] -4-methyl-6- (tert-butyl) phenol (trade name "TINUVIN 326", manufactured by BASF) ), 2- (2H-benzotriazole-2-yl) -4,6-di-tert-pentylphenol (trade name "TINUVIN 328", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name "TINUVIN 329", BA (Manufactured by SF), 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (trade name "TINUVIN 360", A reaction product of methyl 3- (3- (2H-benzotriazole-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 (trade name "TINUVIN 213") manufactured by BASF. , BASF), 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol (trade name "TINUVIN 571", manufactured by BASF), 2- [2-hydroxy-3- ( 3,4,5,6-Tetrahydrophthalimide-methyl) -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 Cipro Chemical Co., Ltd.), 2- (2H-benzotriazole-2-yl) -4-methyl-6- (3, 4,5,6-Tetrahydrophthalimidylmethyl) Phenol (trade name "SEESORB 706", manufactured by Cipro Kasei Co., Ltd.), 2- (4-benzoyloxy-2-hydroxyphenyl) -5-chloro-2H-benzotriazole (4,5,6-tetrahydrophthalimidinemethyl) Cipro Kasei Co., Ltd. trade name "SEESORB 7012BA"), 2-tert-butyl-6- (5-chloro-2H-benzotriazole-2-yl) -4-methylphenol (trade name "KEMISORB 73", Chemipro Kasei , 2,2'-Methylenebis [6- (2H-benzotriazole-2-yl) -4-tert-octylphenol] (trade name "Adecastab LA-31", manufactured by ADEKA Co., Ltd.), 2- ( 2H-benzotriazole-2-yl) -p-cellulose (trade name "Adecastab LA-32", manufactured by ADEKA Co., Ltd.), 2- (5-chloro-2H-benzotriazole-2-yl) -6-tert -Butyl-4-methylphenol (trade name "Adecastab LA-36", manufactured by ADEKA Co., Ltd.) and the like can be mentioned.

The molecular weight of the compound constituting the ultraviolet absorber is preferably 200 to 1500, more preferably 250 to 1200, and further preferably 300 to 1000. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.

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

The content ratio of the ultraviolet absorber is preferably 1 part by weight to 100 parts by weight, more preferably 1 part by weight to 50 parts by weight, and further preferably 5 parts by weight with respect to 100 parts by weight of the gas generating layer. ~ 30 parts by weight. Within such a range, a pressure-sensitive adhesive sheet capable of forming a better deformed portion can be obtained by laser light irradiation.

B-2. Adhesive A
As the pressure-sensitive adhesive A contained in the gas generating layer, the pressure-sensitive pressure-sensitive adhesive A is preferably used. As the pressure-sensitive adhesive A, for example, acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, vinyl alkyl ether-based pressure-sensitive adhesive, silicone-based pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, polyamide-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, and styrene-diene block are all used. Polymerization system adhesives, etc. may be mentioned. Of these, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive is preferable, and an acrylic-based pressure-sensitive adhesive is more preferable. The pressure-sensitive adhesive may be used alone or in combination of two or more.

The acrylic pressure-sensitive adhesive includes, for example, an acrylic pressure-sensitive adhesive based on an acrylic polymer (homopolymer or copolymer) using one or more (meth) acrylic acid alkyl esters as a monomer component. And so on. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth). ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , (Meta) 2-ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) nonyl acrylate, (meth) isononyl acrylate, (meth) decyl acrylate, (meth) isodecyl acrylate, (meth) acrylate Undecyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate , (Meta) acrylic acid nonadecil, (meth) acrylic acid eicosyl and other (meth) acrylic acid C1-20 alkyl esters. Among them, a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 4 to 18 carbon atoms can be preferably used.

The acrylic polymer is a unit corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance, crosslinkability, etc. May include. Examples of such monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride and icotanic anhydride. Acid anhydride monomers such as; (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth) hydroxyhexyl acrylate, (meth) hydroxyoctyl acrylate, (meth) Hydroxyl group-containing monomers such as hydroxydecyl acrylate, hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl methacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropan sulfonic acid. , (Meta) acrylamide Propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acrylic acid group-containing monomers such as oxynaphthalene sulfonic acid; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (N-substituted) amide-based monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylate. Aminoalkyl (meth) acrylate monomers such as aminoethyl and t-butylaminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate. Monomer: Maleimide-based monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide , N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide and other itaconimide-based monomers; N- (meth) acryloyloxymethylene succinimide, N- (meth) accurloyl-6-oxyhexamethylene succinimide, Succinimide-based monomers such as N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyro Vinyls such as lidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholin, N-vinylcarboxylic acid amides, styrene, α-methylstyrene, N-vinylcaprolactam Monomer; Cyanoacrylate monomer such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate; Polyethylene glycol (meth) acrylate, Polypropylene glycol (meth) acrylate, (meth) acrylic acid Glycol-based acrylic ester monomers such as methoxyethylene glycol and methoxypolypropylene glycol (meth) acrylate; heterocycles such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate and silicone (meth) acrylate, halogen atoms and silicon atoms. Acrylic acid ester-based monomers having the above; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol Polyfunctional monomers such as di (meth) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; isoprene, butadiene, Olefin-based monomers such as isobutylene; vinyl ether-based monomers such as vinyl ether and the like can be mentioned. These monomer components may be used alone or in combination of two or more.

Examples of the rubber-based pressure-sensitive adhesive include natural rubber; polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, and styrene-butadiene. -Styrene block copolymer (SBS) rubber, styrene / ethylene / butylene / styrene block copolymer (SEBS) rubber, styrene / ethylene / propylene / styrene block copolymer (SEPS) rubber, styrene / ethylene / propylene block Examples thereof include rubber-based pressure-sensitive adhesives based on polymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, synthetic rubber such as modified products thereof; and the like as a base polymer.

The gas generated from the gas generation layer is preferably a hydrocarbon (preferably an aliphatic hydrocarbon) -based gas. The gas generating layer capable of generating a hydrocarbon-based gas is composed of, for example, a hydrocarbon-based compound as a main component. The gas generation layer preferably does not contain a compound containing a halogen element. If the generated gas is a hydrocarbon-based gas, it is possible to prevent corrosion of electronic parts that are workpieces. Such an effect becomes more remarkable by forming a gas generating layer containing no compound containing a halogen element. The amount of generated ions from the gas generating layer is preferably 10 m / z to 800 m / z, more preferably 11 m / z to 700 m / z, still more preferably 12 m / z to 500 m / z, and particularly. It is preferably 13 m / z to 400 m / z.

The pressure-sensitive adhesive A may contain any suitable additive, if necessary. Examples of the additive include a cross-linking agent, a tackifier (for example, a rosin-based tackifier, a terpene-based tackifier, a hydrocarbon-based tackifier, etc.), and a plasticizer (for example, a trimellitic acid ester-based plasticizer). , Pyromellitic acid ester plasticizer), pigments, dyes, anti-aging agents, conductive materials, antistatic agents, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, etc. ..

Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, and metals. Examples thereof include salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents. Of these, an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent is preferable.

Specific examples of the isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; 2,4- Aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), tri Methylolpropane / hexamethylene diisocyanate trimeric adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL"), isocyanurate of hexamethylene diisocyanate (manufactured by Japan Polyurethane Industry Co., Ltd., trade name "Coronate HX"), etc. Isocyanate adduct; etc. The content of the isocyanate-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength, and is typically 0.1 to 20 parts by weight with respect to 100 parts by weight of the base polymer. It is more preferably 0.5 parts by weight to 10 parts by weight.

Examples of the epoxy-based cross-linking agent include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, and 1,3-bis (N, N-glycidyl aminomethyl) cyclohexane (Mitsubishi Gas). Chemical Co., Ltd., trade name "Tetrad C"), 1,6-hexanediol diglycidyl ether (Kyoeisha Chemical Co., Ltd., trade name "Epolite 1600"), neopentyl glycol diglycidyl ether (Kyoeisha Chemical Co., Ltd., trade name " Epolite 1500NP ”), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name“ Epolite 40E ”), propylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name“ Epolite 70P ”), polyethylene glycol diglycidyl ether (Japan Oil and fat company, product name "Epiol E-400"), polypropylene glycol diglycidyl ether (Japan Oil and Fat Company, product name "Epiol P-200"), sorbitol polyglycidyl ether (manufactured by Nagase ChemteX, product name "Denacol" EX-611 "), glycerol polyglycidyl ether (manufactured by Nagasechemtex, trade name" Denacol EX-314 "), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagasechemtex, trade name" Denacol EX " -512 "), sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipate diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol Examples thereof include -S-diglycidyl ether and epoxy resins having two or more epoxy groups in the molecule. The content of the epoxy-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength, and is typically 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight of the base polymer. It is more preferably 0.03 part by weight to 5 parts by weight.

C. Adhesive Layer The adhesive layer comprises any suitable adhesive B. The pressure-sensitive adhesive B may be a pressure-sensitive pressure-sensitive adhesive B1 or a curable pressure-sensitive adhesive B2.

The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 40 μm, further preferably 1 μm to 30 μm, and particularly preferably 2 μm to 20 μm. Within such a range, it is possible to form an adhesive layer having a preferable adhesive force and functioning well as a gas barrier layer.

Water vapor permeability of the adhesive layer is preferably not 20000g ^/ (m 2 · day) or less, more preferably 10000g ^/ (m 2 · day) or less, more preferably 7000g ^/ (m 2 · day) It is less than or equal to, more preferably 5000 g / (m ² · day) or less, further preferably 4800 g / (m ² · day) or less, and particularly preferably 4500 g / (m ² · day) or less. Within such a range, the pressure-sensitive adhesive layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy. The smaller the water vapor permeability of the pressure-sensitive adhesive layer is, the more preferable it is, but the lower limit thereof is, for example, 100 g / (m ² · day).

The piercing strength of the pressure-sensitive adhesive layer is preferably 10 mN to 3000 mN, more preferably 30 mN to 2500 mN, further preferably 50 mN to 2000 mN, and particularly preferably 100 mN to 2000 mN. Within such a range, the pressure-sensitive adhesive layer functions well as a gas barrier layer, and the shape change due to gas generation preferably occurs, and as a result, a deformed portion having an excellent shape is formed. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy.

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

C-1. Pressure-sensitive adhesive B1
Examples of the pressure-sensitive adhesive B1 include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, and styrene-. Dienblock copolymer system adhesives and the like can be mentioned. Of these, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive is preferable, and an acrylic-based pressure-sensitive adhesive is more preferable. As the pressure-sensitive adhesive B1 contained in the pressure-sensitive adhesive layer containing the pressure-sensitive pressure-sensitive adhesive, the pressure-sensitive adhesive described in Section B-2 can be used.

C-2. Curing adhesive B2
Examples of the curable pressure-sensitive adhesive B2 include a thermosetting type pressure-sensitive adhesive and an active energy ray-curable pressure-sensitive adhesive. Preferably, an active energy ray-curable pressure-sensitive adhesive is used. The pressure-sensitive adhesive layer formed by the active energy ray-curable pressure-sensitive adhesive is a pressure-sensitive adhesive layer formed by irradiating the active energy ray, that is, a pressure-sensitive adhesive layer having a predetermined adhesive strength after irradiation with the active energy ray. Is.

Examples of the resin material constituting the active energy ray-curable pressure-sensitive adhesive include an ultraviolet curing system (written by Kiyomi Kato, published by the General Technology Center (1989)), a photocuring technology (edited by the Technical Information Association (2000)), and special features. Examples thereof include resin materials described in Kai 2003-292916, Japanese Patent No. 4151850, and the like. More specifically, a resin material (B2-1) containing a polymer serving as a base material and an active energy ray-reactive compound (monomer or oligomer), a resin material containing an active energy ray-reactive polymer (B2-2), and the like. Can be mentioned.

Examples of the polymer serving as the base material include natural rubber, polyisobutylene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, recycled rubber, butyl rubber, polyisobutylene rubber, and nitrile rubber (NBR). Examples include rubber-based polymers; silicone-based polymers; acrylic-based polymers. These polymers may be used alone or in combination of two or more.

Examples of the active energy ray-reactive compound include a photoreactive monomer or oligomer having a plurality of functional groups having carbon-carbon multiple bonds such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an acetylene group. .. 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. Since a compound having an ethylenically unsaturated functional group easily generates radicals by ultraviolet rays, it is possible to form a pressure-sensitive adhesive layer that can be cured in a short time by using the compound. Further, if a (meth) acrylic compound having an ethylenically unsaturated functional group is used, a pressure-sensitive adhesive layer having an appropriate hardness can be formed after curing. Specific examples of the photoreactive monomer or oligomer include trimethyl propantri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, urethane Examples thereof include (meth) acryloyl group-containing compounds such as (meth) acrylate-based compounds; and 2 to pentamers of the (meth) acryloyl group-containing compound. These compounds may be used alone or in combination of two or more.

Further, as the active energy ray-reactive compound, a monomer such as epoxidized butadiene, glycidyl methacrylate, acrylamide, vinyl siloxane; or an oligomer composed of the monomer may be used. The resin material (B2-1) containing these compounds can be cured by high-energy rays such as ultraviolet rays and electron beams.

Further, 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 heterocycles in the molecule may be used. In the mixture, the organic salt is cleaved by irradiation with active energy rays (for example, ultraviolet rays and electron beams) to generate ions, which act as a starting species to cause a ring-opening reaction of a heterocycle to form a three-dimensional network structure. Can be done. Examples of the organic salts include iodonium salt, phosphonium salt, antimonium salt, sulfonium salt, borate salt and the like. Examples of the heterocycle in the compound having a plurality of heterocycles in the molecule include oxylane, oxetane, oxolane, thiirane, and aziridine.

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

Examples of the active energy ray-reactive polymer include a polymer having an active energy ray-reactive functional group having a carbon-carbon multiple bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an acetylene group. Preferably, a compound (polymer) having an ethylenically unsaturated functional group is used, and more preferably, a (meth) acrylic polymer having an acryloyl group or a methacryloyl group is used. Specific examples of the polymer having an active energy ray-reactive functional group include a polymer composed of a polyfunctional (meth) acrylate. The polymer composed of the polyfunctional (meth) acrylate preferably has an alkyl ester having 4 or more carbon atoms in a side chain, more preferably has an alkyl ester having 6 or more carbon atoms, and has 8 carbon atoms. It is more preferable to have the above alkyl ester, it is particularly preferable to have an alkyl ester having 8 to 20 carbon atoms, and most preferably to have an alkyl ester having 8 to 18 carbon atoms.

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

The active energy ray-curable pressure-sensitive adhesive can be cured by irradiation with active energy rays. In the pressure-sensitive adhesive sheet of the present invention, the adherend can be adhered by sticking the adherend before curing the pressure-sensitive adhesive and then irradiating the pressure-sensitive adhesive with active energy rays to cure the pressure-sensitive adhesive. Examples of the active energy ray include gamma ray, ultraviolet ray, visible ray, infrared ray (heat ray), radio wave, alpha ray, beta ray, electron beam, plasma flow, ionization ray, particle beam and the like. Conditions such as the wavelength of the active energy ray and the irradiation amount can be set to arbitrary appropriate conditions according to the type of resin material used and the like. For example, the pressure-sensitive adhesive can be cured by irradiating with ultraviolet rays having an irradiation amount of 10 to 1000 mJ / cm ^2.

D. Intermediate layer Examples of the form of the intermediate layer include a resin layer and an adhesive layer.

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 a pressure-sensitive adhesive C composed of a thermoplastic resin, or the like. In another embodiment, 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 curable resin, a layer containing a curable pressure-sensitive adhesive D, or the like.

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

The water vapor permeability of the intermediate layer is preferably 5000 g / (m ² · day) or less, more preferably 4800 g / (m ² · day) or less, and further preferably 4500 g / (m ² · day) or less. It is more preferably 4200 g / (m ² · day) or less. Within such a range, the intermediate layer functions well as a gas barrier layer, and a deformed portion having an excellent shape is formed. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy. While higher water vapor permeability of the intermediate layer is preferably small, its lower limit is, for example, ^{0.1g / (m 2 · day)} .

The piercing strength of the intermediate layer is preferably 300 mN to 5000 mN, more preferably 500 mN to 4500 mN, and further preferably 1000 mN to 4000 mN. Within such a range, the intermediate layer functions well as a gas barrier layer, and the shape change due to gas generation preferably occurs, and as a result, a deformed portion having an excellent shape is formed. By using such an adhesive sheet, a small adherend (for example, an electronic component) can be peeled off with high accuracy.

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

D-1. Intermediate layer as a resin layer The intermediate layer as a 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), ultraviolet curable resin, thermosetting resin, urethane resin, epoxy resin and the like. Can be mentioned. In one embodiment, the resin film is made of 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 further preferably 1 μm to 20 μm.

D-2. Intermediate layer as a layer having adhesiveness Examples of the intermediate layer as a layer having adhesiveness include an intermediate layer containing a pressure-sensitive pressure-sensitive adhesive, an intermediate layer containing a curable pressure-sensitive adhesive, and the like. Preferably, an intermediate layer containing the curable pressure-sensitive adhesive D is arranged. In particular, if the pressure-sensitive adhesive layer containing the pressure-sensitive pressure-sensitive adhesive A and the intermediate layer containing the curable pressure-sensitive adhesive D are combined as the pressure-sensitive adhesive layer, a pressure-sensitive adhesive sheet capable of forming a better deformed portion by laser light irradiation. Can be obtained. As the curable pressure-sensitive adhesive D, the pressure-sensitive adhesive described in Section C-2 can be used.

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

E. Method for Producing Adhesive Sheet The adhesive sheet of the present invention can be produced by any suitable method. In the pressure-sensitive adhesive sheet of the present invention, for example, a composition for forming a gas generation layer containing a pressure-sensitive adhesive A and an ultraviolet absorber is directly applied onto a predetermined base material to form a gas generation layer, and the gas generation layer is formed. A method of forming a pressure-sensitive adhesive layer by applying a composition for forming a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive B can be mentioned. In one embodiment, when the pressure-sensitive adhesive sheet has an intermediate layer, a composition for forming an intermediate layer is applied onto the gas generating layer to form the intermediate layer before forming the pressure-sensitive adhesive layer, and the intermediate layer is formed. The pressure-sensitive adhesive layer forming composition is applied onto the pressure-sensitive adhesive layer to form the pressure-sensitive adhesive layer. Further, each layer may be formed separately and then bonded to form an adhesive sheet.

As the coating method of the above composition, any appropriate coating method can be adopted. For example, after application, it can be dried to form each layer. Examples of the coating method include a coating method using a multi-coater, a die coater, a gravure coater, an applicator, and the like. Examples of the drying method include natural drying and heat drying. The heating temperature for heat-drying can be set to any suitable temperature depending on the characteristics of the substance to be dried. Further, depending on the morphology of each layer, activation energy ray irradiation (for example, ultraviolet irradiation) can be performed.

F. Method for processing electronic components The method for processing electronic components of the present invention is to attach the electronic components to the adhesive sheet and to irradiate the adhesive sheet with laser light to peel off the electronic components from the adhesive sheet. including. Examples of electronic components include semiconductor chips, LED chips, MLCCs, and the like.

The peeling of the electronic components can be performed regioselectively. Specifically, a plurality of electronic components may be attached and fixed to an adhesive sheet, a part of the electronic component may be peeled off, and the other electronic components may be peeled off so as to remain fixed. ..

In one embodiment, the method for processing an electronic component of the present invention is to perform a predetermined process on the electronic component after the electronic component is attached to the adhesive sheet and before the electronic component is peeled off from the adhesive sheet. Including. The above processing is not particularly limited, and for example, processing such as grinding processing, dicing processing, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, inspection, cleaning, transfer, arrangement, repair, and device surface protection. Can be mentioned.

The electronic component size (the area of the bonded surface) is, for example, 1μm ² ~ 250000μm ^2. In one embodiment, the size of the electronic component (the area of the bonded surface) the electronic component of 1μm ² ~ 6400μm ² may be subjected to treatment. In another embodiment, electronic components having an electronic component size (area of attachment surface) of 1 μm ² to 2500 μm ² may be subjected to processing.

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

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

In one embodiment, the method for processing an 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.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The evaluation method in the examples is as follows. In the following evaluation, an adhesive sheet from which the separator was peeled off was used. Further, in the examples, unless otherwise specified, "parts" and "%" are based on weight.

(1) Transmittance In the case of an adhesive sheet having an intermediate layer, the adhesive sheet is set in a spectrophotometer (trade name "UV-VIS ultraviolet-visible spectrophotometer SolidSpec3700", manufactured by Shimadzu Corporation), and the incident light is emitted. The light transmittance in the wavelength region of 300 nm to 800 nm was measured so as to be vertically incident on the gas barrier layer side of the sample. The transmittance of the obtained transmission spectrum at a wavelength of 360 nm was extracted. In the case of an adhesive sheet consisting of only an adhesive layer, set it on a spectrophotometer with one release liner left and measure it, and then measure the transmission spectrum of the release liner alone and subtract it to make it adhesive. The transmission spectrum of the layer alone was obtained. The transmittance of the obtained transmission spectrum at a wavelength of 360 nm was extracted.

(2) Maximum gas generation peak temperature About 0.5 mg of the pressure-sensitive adhesive sheet sample was set in a heating furnace type pyrolyzer, and a mass chromatogram was obtained by EGA-MS analysis in which the components volatilized by heating were mass-analyzed. A heating furnace type pyrolyzer (manufactured by Frontier Lab, trade name "PY2020iD") raises the temperature from 40 ° C to 500 ° C at a heating rate of 10 ° C / min, and a GC / MS analyzer (manufactured by JEOL, trade name "JMS"). -T100GCV ") was used to calculate the maximum gas generation peak temperature from a mass chromatogram in the mass range m / z = 10 to 800.

(3) Gasification start temperature The temperature of the pressure-sensitive adhesive sheet was raised by the same method as in (2) above, and the gas generation start temperature calculated from the EGA analysis was used as the gasification start temperature. The gas generation rise temperature is defined as the temperature at which half of the maximum gas generation peak of the EGA / MS chromatogram obtained from EGA analysis is reached.

(4) Generated gas type The adhesive sheet sample was set in an automatic sample combustion device (manufactured by Mitsubishi Chemical Analytech Co., Ltd., trade name "AQF-2100H") and heated at 400 ° C. for 30 minutes to collect the generated gas. By analyzing the collected liquid by ion chromatography, the generated gas species was identified.

(5) 5% weight loss temperature differential thermal analyzer using (TA Instruments Inc., trade name "Discovery TGA"), the pressure-sensitive adhesive sheet heated temperature 10 ° C. / min, _{N 2} atmosphere, flow rate 25 ml / min The temperature at which the weight was reduced by 5% was measured.

(6) 10% weight loss temperature differential thermal analyzer using (TA Instruments Inc., trade name "Discovery TGA"), the pressure-sensitive adhesive sheet heated temperature 10 ° C. / min, _{N 2} atmosphere, flow rate 25 ml / min The temperature at which the weight was reduced by 10% was measured.
The 10% weight loss temperature was measured for each of the pressure-sensitive adhesive sheet and the gas generating layer (UV absorber).

(7) Water vapor permeability A sample is prepared by pasting a sample so as to cover the opening of an Al jig having an opening of 10 mm × 10 mm, and a water vapor permeability measuring device (manufactured by MOCON, trade name “PERMATRAN-” A measurement sample was placed between the first chamber and the second chamber of W3 / 34G ") and evaluated by the MOCON measurement method. The temperature and humidity conditions were 30 ° C./90% RH, the gas (water vapor) flow rate was 10.0 ± 0.5 cc / min, and the measurement time was 20 hours.
The water vapor transmittance was measured for each of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer, and the intermediate layer.

(8) Change in surface shape A glass plate (manufactured by Matsunami Glass Co., Ltd., large slide glass S9112 (standard large white edge polishing No. 2)) is attached to the gas generation layer side (opposite side of the adhesive layer) of the adhesive sheet. A measurement sample was obtained. From the glass plate side of the measurement sample, a pulse scan was performed at 0.80 mW output and a frequency of 40 kHz using UV laser light having a wavelength of 355 nm and a beam diameter of about 20 μmφ to generate gas from the gas generating layer. The surface of the pressure-sensitive adhesive layer corresponding to any one spot pulse-scanned was observed with a confocal laser scanning microscope 1 minute after the laser light irradiation, and the vertical displacement Y and the horizontal displacement X (diameter; half-value full width) were measured.
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); When is less than 0.6 μm, the peelability is insufficient (x in the table).

(9) Adhesive strength (gas generation layer side)
PET # 25 was attached to the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet to obtain a measurement sample. The adhesive force of the measurement sample to the SUS430 on the gas generation layer side was measured by a method according to JIS Z 0237: 2000 (bonding conditions: 2 kg roller 1 reciprocation, tensile speed: 300 mm / min, peeling angle 180 °).

(10) Adhesive strength (adhesive layer)
PET # 25 was attached to the gas generating layer side of the pressure-sensitive adhesive sheet to obtain a measurement sample. The adhesive strength of the measurement sample to the SUS430 on the adhesive layer side was measured by a method according to JIS Z 0237: 2000 (bonding conditions: 2 kg roller 1 reciprocation, tensile speed: 300 mm / min, peeling angle 180 °).

(11) In-plane uniformity of deformation The gas generating layer was irradiated with UV laser light as described in (8) above.
Observe the deformed part in the 2 mm × 2 mm range randomly selected with a microscope, and if 90% or more of the convex parts are the same size, it is good (○ in the table), 80% or more and less than 90% of the convex parts. Was acceptable (in the table, Δ) when they had the same size, and bad (x in the table) when less than 80% of the convex parts had the same size. The same size means that the difference in displacement X is within ± 20%.

(12) Regioselectivity of deformation The gas generating layer was irradiated with UV laser light as described in (8) above.
The case where only the laser light irradiation part was deformed in a single manner was regarded as acceptable (◯), and the case where multiple deformations were also made around the laser irradiation part was regarded as unacceptable (×).

(13) Elastic modulus Using a nanoindenter (Titanium Inc. Triboinder TI-950), a single indentation method at a predetermined temperature (25 ° C.) is used to indent the indentation speed of about 500 nm / sec, the withdrawal speed of about 500 nm / sec, and indentation. The elastic modulus of the cross section of the gas generating layer was measured under the measurement conditions at a depth of about 1500 nm.

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

[Production Example 2] Preparation of Adhesive b 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 are added to ethyl acetate, and then 70 parts by weight. The mixture was heated to ° C. to obtain an ethyl acetate solution of an acrylic copolymer (polymer A2).
Ethyl acetate solution of polymer A2 (polymer A2: 100 parts by weight), epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals, trade name "TETRAD-C") by 1 part by weight, and isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., The pressure-sensitive adhesive b was prepared by mixing with 3 parts by weight of the trade name “Coronate L”). The composition of the pressure-sensitive adhesive b is shown in Table 1.

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

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

[Production Example 4] Preparation of composition a for forming an intermediate layer In ethyl acetate, 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of methyl acrylate, 10 parts by weight of acrylic acid, and benzoyl peroxide 0 as a polymerization initiator. After adding 2 parts by weight, the mixture was heated to 70 ° C. to obtain an ethyl acetate solution of the acrylic copolymer (polymer B).
Ethyl acetate solution of polymer B (polymer B: 100 parts by weight), epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals, trade name "Tetrad C"), 1 part by weight, UV oligomer (manufactured by Mitsubishi Chemicals, trade name "Shikou" UV-1700B ") 50 parts by weight and 3 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name" Omnirad 127 ") were mixed to prepare a composition a for forming an intermediate layer. The composition of the intermediate layer forming composition a is shown in Table 2.

[Production Example 5] Preparation of composition b for forming an intermediate layer Maleic acid-modified styrene / ethylene / butylene / styrene block copolymer (SEBS: styrene moiety / ethylene / butylene moiety (weight ratio) = 30/70, acid value: 10 (mg-CH ₃ ONa / g), manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "Tuftec M1913") 100 parts by weight, and epoxy-based surfactant (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C") 3 parts by weight 3 parts by weight of a fatty acid ester-based surfactant (manufactured by Kao, trade name "Exepearl IPP", molecular weight: 298.5, number of carbon atoms of alkyl group: 16) and toluene as a solvent are mixed and intermediate. A layer-forming composition b was obtained. The composition of the intermediate layer forming composition b is shown in Table 2.

[Production Example 6] Preparation of Composition a for Forming Gas Generation Layer Polymer A was obtained in the same manner as in Production Example 1.
A toluene solution of polymer A (polymer A: 100 parts by weight), an isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L") 1.5 parts by weight, and an ultraviolet absorber (manufactured by BASF, trade name "Tinuvin 477"). 20 parts by weight was mixed to prepare a composition a for forming a gas generating layer. The composition of the composition a for forming a gas generating layer is shown in Table 3.

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

[Production Example 8] Preparation of composition c for forming a gas generating layer As a UV absorber, 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1, A composition for forming a gas generating layer c was prepared in the same manner as in Production Example 5, except that 10 parts by weight of 3,5-triazine (trade name “TINUVIN 460”, manufactured by BASF) was used. The composition of the composition for forming the gas generation layer c is shown in Table 3.

[Production Example 9] Preparation of composition d for forming a gas generating layer As a UV absorber, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl)- Manufactured except using 20 parts by weight of the reaction product of 5-hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxylane (trade name "TINUVIN 400", manufactured by BASF). The composition d for forming a gas generating layer was prepared in the same manner as in Example 5. The composition of the composition d for forming a gas generation layer is shown in Table 3.

[Production Example 10] Preparation of composition e for forming a gas generating layer As a UV absorber, 2- [5-chloro-2H-benzotriazole-2-yl] -4-methyl-6- (tert-butyl) phenol ( The composition e for forming a gas generating layer was prepared in the same manner as in Production Example 5 except that 20 parts by weight of the trade name “TINUVIN 326” (manufactured by BASF) was used. The composition of the composition e for forming the gas generation layer is shown in Table 3.

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

[Production Example 12] Preparation of composition g for forming a gas generating layer In ethyl acetate, 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 are added. After the addition, the mixture was heated to 70 ° C. to obtain an ethyl acetate solution of the acrylic copolymer (polymer C).
An ethyl acetate solution of polymer C (polymer C: 100 parts by weight), an isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L") by 1 part by weight, and an ultraviolet absorber (manufactured by BASF, trade name "Tinuvin 477"). 20 parts by weight was mixed to prepare a composition g for forming a gas generating layer. The composition of the composition g for forming the gas generation layer is shown in Table 3.

[Production Example 13] Preparation of composition h for forming a gas generating layer In ethyl acetate, 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 are added. After the addition, the mixture was heated to 70 ° C. to obtain an ethyl acetate solution of the acrylic copolymer (polymer C).
Ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 0.1 part by weight of epoxy cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD-C"), and ultraviolet absorber (manufactured by BASF, Inc., The composition h for forming a gas generating layer was prepared by mixing with 20 parts by weight of the trade name “Tinuvin 477”). The composition of the composition h for forming the gas generation layer is shown in Table 3.

[Production Example 14] Preparation of composition i for forming a gas generating layer Maleic acid-modified styrene / ethylene / butylene / styrene block copolymer (SEBS: styrene moiety / ethylene / butylene moiety (weight ratio) = 30/70, acid value : 10 (mg-CH ₃ ONa / g), manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "Tuftec M1913") 100 parts by weight, and epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C") 3 weights 20 parts by weight of an ultraviolet absorber (manufactured by BASF, trade name "Tinuvin477") and toluene as a solvent were mixed to prepare a composition i for forming a gas generating layer. The composition of the composition i for forming a gas generation layer is shown in Table 3.

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

[Production Example 16] Preparation of heat-expandable microsphere-containing composition I The amount of the cross-linking agent blended is 1.4 parts by weight without blending an ultraviolet absorber, and the heat-expandable microspheres (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., product) Production example except that 30 parts by weight of the name "Matsumoto Microsphere F-50D") and 10 parts by weight of the terpenphenol-based tackifier resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name "Sumilite Resin PR51732") are blended. The heat-expandable microsphere-containing composition I was prepared in the same manner as in 5.

[Production Example 17] Preparation of Heat-Expandable Microsphere-Containing Composition II Terpene Phenol Adhesive Resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name "Sumilite Resin PR51732") Instead of 10 parts by weight, terpene phenolic tackifier resin (Manufactured by Yasuhara Chemical Co., Ltd., trade name “YS Polystar T160”) A heat-expandable microsphere-containing composition II was prepared in the same manner as in Production Example 13 except that 20 parts by weight was used.

[Production Example 14'] Preparation of composition j for forming a gas generating layer In ethyl acetate, 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. Was heated to 70 ° C. to obtain an ethyl acetate solution of the acrylic copolymer (polymer C).
Ethyl acetate solution of polymer C (polymer C: 100 parts by weight), 1 part by weight of isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), and epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals, Inc., product) A composition j for forming a gas generating layer was prepared by mixing 0.1 part by weight of the name "TETRAD-C") and 10 parts by weight of an ultraviolet absorber (manufactured by BASF, trade name "TINUVIN 400"). The composition of the composition j for forming a gas generation layer is shown in Table 3.

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

[Example 1]
The pressure-sensitive adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate film (thickness: 75 μm) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) was 15 μm, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
The composition a for forming a gas generating layer obtained in Production Example 5 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm), and the thickness after solvent volatilization (drying). Was applied so as to have a thickness of 7 μm, and then dried to form a gas generation layer precursor layer a on the polyethylene terephthalate film.
The pressure-sensitive adhesive layer precursor layer a and the gas generation layer precursor layer a are laminated and bonded between rolls, and a pressure-sensitive adhesive sheet (adhesive layer / gas generation layer) sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. ) Was obtained.
The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 4.

[Example 2]
The pressure-sensitive adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate film (thickness: 75 μm) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) was 15 μm, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
The composition a for forming an intermediate layer obtained in Production Example 3 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm), and the thickness after solvent volatilization (drying) is increased. The film was applied to a thickness of 15 μm and then dried to form an intermediate layer precursor layer a on the polyethylene terephthalate film.
Next, the pressure-sensitive adhesive layer precursor layer a and the intermediate layer precursor layer a are laminated and bonded between rolls ^{, and UV-irradiated from the intermediate layer precursor layer side under the condition of 500 mJ / cm 2} , and treated with a silicone release agent. A laminate precursor layer a sandwiched between surfaced polyethylene terephthalate films was obtained.
The composition a for forming a gas generating layer obtained in Production Example 5 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm), and the thickness after solvent volatilization (drying). Was applied so as to have a thickness of 7 μm, and then dried to form a gas generation layer precursor layer a on the polyethylene terephthalate film.
After peeling off the polyethylene terephthalate film with a silicone release agent-treated surface on the intermediate layer precursor layer a side of the laminate precursor layer a, the intermediate layer precursor layer a of the laminate precursor layer a and the gas generation layer precursor layer a are separated. By laminating and laminating between the rolls, 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 subjected to the above evaluations (1) to (12). The results are shown in Table 4.

[Example 3]
The pressure-sensitive adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate film (thickness: 75 μm) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) was 15 μm, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
The composition b for forming the intermediate layer obtained in Production Example 4 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm), and the thickness after solvent volatilization (drying) is increased. The film was applied to a thickness of 15 μm and then dried to form an intermediate layer precursor layer a on the polyethylene terephthalate film.
Next, the pressure-sensitive adhesive layer precursor layer a and the intermediate layer precursor layer b were laminated and bonded between rolls to obtain a laminate precursor layer b sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface. ..
The composition a for forming a gas generating layer obtained in Production Example 5 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm), and the thickness after solvent volatilization (drying). Was applied so as to have a thickness of 7 μm, and then dried to form a gas generation layer precursor layer a on the polyethylene terephthalate film.
After peeling off the polyethylene terephthalate film with a silicone release agent-treated surface on the intermediate layer precursor layer b side of the laminate precursor layer b, the intermediate layer precursor layer b of the laminate precursor layer b and the gas generation layer precursor layer a are separated. By laminating and laminating between the rolls, 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 subjected to the above evaluations (1) to (12). The results are shown in Table 4.

[Example 4]
The pressure-sensitive adhesive a obtained in Production Example 1 was applied to a polyethylene terephthalate film (thickness: 75 μm) with a silicone release agent-treated surface so that the thickness after solvent volatilization (drying) was 15 μm, and then dried. , The pressure-sensitive adhesive layer precursor layer a was formed on the polyethylene terephthalate film.
The composition a for forming a gas generating layer obtained in Production Example 5 is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm), and the thickness after solvent volatilization (drying). Was applied so as to have a thickness of 7 μm, and then dried to form a gas generation layer precursor layer a on the polyethylene terephthalate film.
The adhesive layer precursor layer a was laminated between rolls on one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumirror # 2F51N", thickness: 2 μm).
Next, the gas generating layer precursor layer a was laminated and bonded between the rolls on the side opposite to the pressure-sensitive adhesive layer precursor layer a of the polyethylene terephthalate film.
In this way, an adhesive sheet (adhesive layer / intermediate layer / gas generating layer) sandwiched between polyethylene terephthalate films with a silicone release agent-treated surface was obtained.
The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 4.

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

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

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

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

[Example 9]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the pressure-sensitive adhesive layer was set to 1 μm and the thickness of the gas generating layer was set to 10 μm. The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 5.

[Example 10]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the pressure-sensitive adhesive layer was set to 1 μm and the thickness of the gas generating layer was set to 15 μm. The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 5.

[Example 11]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the pressure-sensitive adhesive layer was set to 5 μm and the thickness of the gas generating layer was set to 5 μm. The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 5.

[Example 12]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the pressure-sensitive adhesive layer was set to 10 μm and the thickness of the gas generating layer was set to 5 μm. The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 5.

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

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

[Example 15]
The composition h for forming a gas generating layer is coated on one surface of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness: 50 μm) so that the thickness after solvent volatilization (drying) is 20 μm. To form a gas generating layer.
Next, the adhesive b is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm) so that the thickness after solvent volatilization (drying) is 10 μm. , A pressure-sensitive adhesive layer was formed.
Next, the gas generating layer and the pressure-sensitive adhesive layer were laminated to obtain a pressure-sensitive adhesive sheet (adhesive layer / gas-generating layer / base material) protected by a polyethylene terephthalate film with a silicone release agent-treated surface.
The obtained adhesive sheet was subjected to the above evaluation. The results are shown in Table 6.

[Example 16]
An adhesive sheet was obtained in the same manner as in Example 14 except that the gas generating layer forming composition i was used instead of the gas generating layer forming composition h. The obtained adhesive sheet was subjected to the above evaluation. The results are shown in Table 6.

[Example 17]
A composition for forming a gas generating layer j is coated on one surface of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumirror S10", thickness: 50 μm) so that the thickness after solvent volatilization (drying) is 20 μm. To form a gas generating layer.
Next, the adhesive a is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Toray Industries, Inc., trade name "Therapeu", thickness: 38 μm) so that the thickness after solvent volatilization (drying) is 5 μm. , A pressure-sensitive adhesive layer was formed.
Next, the gas generating layer and the pressure-sensitive adhesive layer were laminated to obtain a pressure-sensitive adhesive sheet (adhesive layer / gas-generating layer / base material) protected by a polyethylene terephthalate film with a silicone release agent-treated surface.
The obtained adhesive sheet was subjected to the above evaluation. The results are shown in Table 6.

[Example 18]
An adhesive sheet was obtained in the same manner as in Example 17 except that the gas generating layer forming composition k was used instead of the gas generating layer forming composition j. The obtained adhesive sheet was subjected to the above evaluation. The results are shown in Table 6.

 

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

[Comparative Example 2]
The pressure-sensitive adhesive I is used instead of the pressure-sensitive adhesive a, the thickness of the pressure-sensitive adhesive layer is 10 μm, a PET film having a thickness of 188 μm is used as an intermediate layer, and a heat-expandable microsphere is contained instead of the composition a for forming a gas generating layer. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4 except that a 48 μm gas generating layer was formed using the composition I. The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 7.

[Comparative Example 3]
The pressure-sensitive adhesive I is used instead of the pressure-sensitive adhesive a, the thickness of the pressure-sensitive adhesive layer is 10 μm, a PET film having a thickness of 100 μm is used as an intermediate layer, and a heat-expandable microsphere is contained instead of the composition a for forming a gas generating layer. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4 except that a 48 μm gas generating layer was formed using Composition II. The obtained adhesive sheet was subjected to the above evaluations (1) to (12). The results are shown in Table 7.

10 Gas generating layer 20 Adhesive layer 30 Intermediate layer 100, 200 Adhesive sheet

Claims (17)

1. A pressure-sensitive adhesive sheet comprising a gas-generating layer and at least one pressure-sensitive adhesive layer arranged on one side of the gas-generating layer.
   The pressure-sensitive adhesive layer is a layer whose surface is deformed by irradiating the pressure-sensitive adhesive sheet with laser light.
   Adhesive sheet.
2. The adhesive sheet according to claim 1, wherein the gas generating layer is a layer capable of absorbing ultraviolet rays.
3. The adhesive sheet according to claim 2, wherein the gas generating layer contains an ultraviolet absorber.
4. The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the thickness of the gas generating layer is 0.1 μm to 50 μm.
5. The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the gas generating layer is a layer for generating a hydrocarbon-based gas.
6. The adhesive sheet according to any one of claims 1 to 5, wherein the gasification start temperature of the gas generation layer is 150 ° C to 500 ° C.
7. Any one of claims 1 to 6, wherein the elastic modulus Er (gas) [unit: MPa] and the thickness h (gas) [unit: μm] of the gas generating layer by the nanoindentation method satisfy the following formula (1). Adhesive sheet described in.
   Log (Er (gas) × 10 ⁶ ) ≧ 8.01 × h (gas) ^-0.116 ... (1)
8. The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive layer has a thickness of 0.1 μm to 50 μm.
9. The pressure-sensitive adhesive sheet according to any one of claims 1 to 8, wherein the amount of deformation of the surface of the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive sheet with laser light is 0.6 μm or more in the vertical displacement of the pressure-sensitive adhesive layer.
10. The adhesive sheet according to any one of claims 1 to 9, wherein the ultraviolet transmittance at a wavelength of 360 nm is 30% or less.
11. The adhesive sheet according to any one of claims 1 to 10, wherein the 10% weight loss temperature is 200 ° C. to 500 ° C.
12. The adhesive sheet according to any one of claims 1 to 11, wherein the water vapor transmittance is 5000 g / (m ^{2 · day) or less.}
13. An electron including sticking an electronic component on the pressure-sensitive adhesive sheet according to any one of claims 1 to 12 and irradiating the pressure-sensitive adhesive sheet with laser light to peel off the electronic component from the pressure-sensitive adhesive sheet. How to handle parts.
14. The method for processing an electronic component according to claim 13, wherein the electronic component is peeled off in a regioselective manner.
15. After the electronic component is attached to the adhesive sheet and before the electronic component is peeled off from the adhesive sheet,
    Including performing a predetermined process on the electronic component,
    The method for processing an electronic component according to claim 13 or 14.
16. 15. The treatment according to claim 15, wherein the treatment is grinding, dicing, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, inspection, cleaning, transfer, arrangement, repair or device surface protection. How to process electronic components.
17. The method for processing an electronic component according to any one of claims 13 to 16, which comprises arranging the electronic component on another sheet after peeling the electronic component from the adhesive sheet.
    

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