TW202126769A - Pressure-sensitive adhesive sheet - Google Patents

Abstract

Provided is a pressure-sensitive adhesive sheet with which small-sized electronic components (e.g., chips having a size of 50 [mu]m□ or less) can be temporarily fixed satisfactorily and removed satisfactorily. This pressure-sensitive adhesive sheet includes a pressure-sensitive adhesive layer comprising an actinic-ray-curable pressure-sensitive adhesive, and has a transmittance for light having a wavelength of 360 nm of 0-35% and a transmittance for light having a wavelength of 380 nm of 10-100%. One embodiment of the pressure-sensitive adhesive sheet, which has been applied to a stainless-steel sheet, has an initial adhesive force at 23 DEG C of 0.3-15 N/20 mm. Another embodiment of the pressure-sensitive adhesive sheet, which has been applied to a stainless-steel sheet and then irradiated with ultraviolet light in an amount of 460 mJ/cm2, has an initial adhesive force at 23 DEG C of 0.01-2.4 N/20 mm.

Description

Adhesive sheet

The present invention relates to an adhesive sheet.

Previously, when processing and transferring electronic parts, there were cases where the following operations were performed, that is, the electronic parts were temporarily fixed to the adhesive sheet during processing, transfer, etc., and the electronic parts were adhered from there after processing and transfer. The sheet peels off. As the adhesive sheet used in this operation, there are cases where the following adhesive sheet is used. The adhesive sheet has a specific adhesive force during processing and transfer (when electronic parts are received), and after processing and transfer ( When electronic parts are handed over) the adhesive force can be reduced. As one of such adhesive sheets, there is proposed an adhesive sheet formed by including thermally expandable microspheres in an adhesive layer (for example, Patent Document 1). The adhesive sheet containing heat-expandable microspheres has the following characteristics: it has a specific adhesive force, and by using heating to expand the heat-expandable microball disappear. This kind of adhesive sheet has the advantage that the adherend can be easily peeled off without external stress.

However, in recent years, along with the trend toward lighter weights of various devices and an increase in the number of devices mounted, the miniaturization of electronic components has been promoted, and it has become necessary to temporarily fix electronic components that are downsized to the same size as the above-mentioned thermally expandable microspheres. . When temporarily fixing (receiving) electronic parts that have been miniaturized and then peeling (handing over) them, temporarily fixing requires higher adhesion than electronic parts of normal sizes. When peeling off, you need to select a narrower range Sexual performance peeling. However, the conventional adhesive sheet has the following problem: if the adhesive force is increased, the releasability will be deteriorated, on the other hand, if the adhesive force is decreased, the temporary fixability will be deteriorated. Also, when temporarily fixing an electronic component that has been miniaturized and then peeling it off (handing over), due to the deviation of the particle size, there are places where there are thermally expandable microspheres with a larger particle size, and where there are no thermally expandable microspheres. The influence of the others becomes larger, and it exists in the situation where good peeling cannot be performed on the part. Prior art literature Patent literature

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

[The problem to be solved by the invention]

The present invention was completed in order to solve the aforementioned problems, and its object is to provide an adhesive sheet that can temporarily fix small electronic parts (for example, a chip with a size of 50 μm□ or less) and can be peeled off well. [Technical means to solve the problem]

The adhesive sheet of the present invention is provided with an adhesive layer containing an active energy ray hardening adhesive, and has a light transmittance of 0% to 35% at a wavelength of 360 nm, and a light transmittance of 10% to 100% at a wavelength of 380 nm . In one embodiment, the initial adhesive force at 23° C. when the adhesive layer of the adhesive sheet is attached to the stainless steel plate is 0.3 N/20 mm to 15 N/20 mm. In one embodiment, the adhesive layer of the adhesive sheet is attached to a stainless steel plate and irradiated with 460 mJ/cm ² of ultraviolet rays. The adhesive force at 23° C. is 0.01 N/20 mm to 2.4 N/20 mm. In one embodiment, the adhesive layer of the adhesive sheet is attached to a stainless steel plate and ^{the adhesive force at 23° C. after irradiating 460 mJ/cm 2} of ultraviolet rays is less than 50% relative to the initial adhesive force. In one embodiment, the light transmittance of the adhesive sheet with a wavelength of 500 nm is 70%-100%. In one embodiment, the haze value of the adhesive sheet is 50% or less. In one embodiment, the adhesive layer contains an ultraviolet absorber, and the maximum absorption wavelength of the ultraviolet absorber is 350 nm or less. In one embodiment, the above-mentioned ultraviolet absorber is the following compound: the compound has a structure in which three benzene rings are bonded to the three benzene rings, and the total number of highly anionic atoms directly bonded to the three benzene rings Less than six. In one embodiment, the adhesive layer contains a photopolymerization initiator, and the absorbance coefficient of the photopolymerization initiator at a wavelength of 365 nm is 10 ml/g·cm to 10000 ml/g·cm. In one embodiment, the adhesive layer contains a photopolymerization initiator, and the absorbance coefficient of the photopolymerization initiator at a wavelength of 405 nm is 10 ml/g·cm or less. In one embodiment, the adhesive layer is cured by irradiating ultraviolet rays of 350 nm or more and 380 nm or less. In one embodiment, the thickness of the adhesive layer is 0.1 μm-50 μm. In one embodiment, the surface of the adhesive sheet is deformed by irradiation with laser light. In one embodiment, the surface of the adhesive sheet is deformed into a convex shape by being irradiated with laser light. In one embodiment, the surface of the adhesive sheet is deformed into a concave shape by irradiation with laser light. According to another aspect of the present invention, a processing method of electronic components is provided. The processing method of the electronic component includes: for the above-mentioned adhesive sheet, attach the electronic component to the adhesive sheet and fix it, process the electronic component, and irradiate the entire adhesive layer of the adhesive sheet with active energy rays to make The adhesive strength of the adhesive sheet decreases, and then, laser light is irradiated to the part that needs to be peeled to peel off the electronic parts. In one embodiment, the peeling of the above-mentioned electronic components is performed at selected positions. In one embodiment, the above-mentioned processing is grinding processing, cutting processing, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer, arrangement, repair, or device surface protection. In one embodiment, the processing method includes: after peeling the electronic component from the adhesive sheet, arranging the electronic component on another sheet. [Effects of Invention]

According to the present invention, it is possible to provide an adhesive sheet that can temporarily fix small electronic parts (for example, a chip with a size of 50 μm or less), and is equipped with a gas generating layer that can generate gas by irradiation with laser light , So that the small electronic parts can be peeled off well.

A. Outline of Adhesive Sheet Fig. 1(a) is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention. The adhesive sheet 100 of this embodiment includes an adhesive layer 10. The adhesive layer 10 contains an active energy ray-curable adhesive. Fig. 1(b) is a schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention. The adhesive sheet 100 ′ of this embodiment further includes a substrate 20, and an adhesive layer 10 is disposed on at least one side of the substrate 20. Although not shown, the adhesive sheet of the present invention may be provided with a release liner on the outer side of the adhesive layer for the purpose of protecting the adhesive surface during the period before use. In addition, as long as the effect of the present invention can be obtained, the adhesive sheet may further include any appropriate other layer. In one embodiment, as shown in FIG. 1(a), the adhesive sheet of the present invention is composed of only one adhesive layer. In other embodiments, as shown in FIG. 1(b), the adhesive sheet of the present invention includes a substrate and an adhesive layer, and the adhesive layer is directly (ie, without intervening other layers) disposed on the substrate. In the present invention, as described later, the adherend can be peeled off well due to the decrease and deformation of the adhesive layer's adhesive force. Therefore, it is not necessary to provide a layer other than the adhesive layer for separating the adherend from the adhesive sheet ( The so-called separation layer) constitutes an adhesive sheet. Also, although not shown, the above-mentioned adhesive layer may be arranged on one side of the substrate, and another adhesive layer may be arranged on the other side of the substrate. The shape of the other adhesive layer is not limited, and it can be a hardened adhesive layer or a pressure-sensitive adhesive layer.

The light transmittance of the adhesive sheet of the present invention at a wavelength of 360 nm is 0% to 35%, preferably 0% to 30%, more preferably 0.01% to 20%, and still more preferably 0.02% to 10%. In addition, the light transmittance of the above-mentioned adhesive sheet at a wavelength of 380 nm is 10%-100%, preferably 20%-90%, more preferably 30%-85%, and still more preferably 45%-80%. Furthermore, the so-called light transmittance of the adhesive sheet is the light transmittance in the thickness direction of the adhesive sheet, and is the light transmittance measured with all the constituent layers of the adhesive sheet as an object. For example, by making the adhesive layer contain a specific ultraviolet absorber, it is possible to form an adhesive sheet whose light transmittance is adjusted in this way.

In the present invention, the adhesive layer contains an active energy ray-curable adhesive (that is, an active energy ray-curable adhesive layer is formed), and ultraviolet rays (ultraviolet rays with a wavelength of 360 nm and ultraviolet rays with a wavelength of 380 nm) are transmitted through When the ratio falls within the above range, the adherend can be peeled off by laser light irradiation in a small range. In more detail, by irradiating the adhesive layer with laser light, the gas generated by the decomposition of the ultraviolet absorber and/or the gas generated by the decomposition of the adhesive layer caused by the heat of the ultraviolet absorber makes the surface of the adhesive sheet (for example, adhesive The surface of the agent layer is deformed, and as a result, the part irradiated with the laser light exhibits releasability. According to the present invention, deformation can be generated in a small range as described above, and therefore, when processing an extremely fine and small adherend, the adherend can also be peeled off well. In addition, even when the small adherend that needs to be peeled off is temporarily fixed adjacent to the small adherend that does not need to be peeled off, the peeling can be performed at the portion to be peeled off, and the peeling is not performed on the portion outside the peeled off object, that is, , Can only peel off small adherends that need to be peeled off, and prevent unnecessary detachment of small adherends. The adhesive sheet of the present invention can exhibit such excellent peelability as one reason, and can improve the adhesiveness before peeling. As a result, when it is necessary to fix the adherend, it can exhibit excellent fixability, and even if the adherend is small, it can be handled without any defects. In addition, the adhesive sheet has excellent directivity at the time of peeling, and it can be peeled only at a desired location, and it is also advantageous in terms of preventing breakage and having less paste residue. Furthermore, the directivity at the time of peeling refers to the index of the positional accuracy when the adherends such as small electronic parts are peeled from the adhesive sheet and aligned at a certain distance away from the adhesive sheet. If the directivity is excellent, then Prevent the adherend from flying out of the expected direction during peeling.

The so-called deformation of the adhesive sheet refers to the displacement generated in the normal direction (thickness direction) and the horizontal direction (direction orthogonal to the thickness direction) of the surface of the adhesive sheet (for example, the surface of the adhesive layer). The deformation of the adhesive sheet is generated by, for example, the following method: by using a UV (ultraviolet) laser with a wavelength of 355 nm and a beam diameter of about 20 μmϕ, pulse scanning is performed at a power of 0.80 mW and a frequency of 40 kHz, and the gas The generating layer generates gas. Regarding the deformed shape, for example, for any one point scanned by the pulse, one minute after the laser light is irradiated, it is observed by measurement by a confocal laser microscope or a non-contact interference microscope (WYKO). The shape can be foamed (convex), through-hole (concave-convex), concave (concave), and releasability can be produced by these deformations. When the electronic parts are to be peeled off efficiently in the normal direction, it is preferable that the displacement in the normal direction before and after the laser light irradiation has a large change, and it is especially suitable for the foamed shape.

In addition, when the adhesive sheet of the present invention in which the adhesive layer contains an active energy ray hardening type adhesive is irradiated with active energy rays, the adhesive force of the entire adhesive layer decreases. By irradiating active energy rays to the entire adhesive layer of the adhesive sheet to which the adherend is attached, after the adhesive force is reduced, laser light is irradiated in the manner described above, which exhibits excellent peeling properties and can prevent The paste remains after peeling. In addition, by forming an adhesive layer containing an active energy ray-curable adhesive, the laser power during peeling can be reduced. The adhesive sheet of the present invention uses low-power laser light to exhibit peelability. Therefore, if the adhesive sheet is used, the damage to the adherend during peeling can be reduced, and the damage of the adherend can be prevented. Examples of active energy rays include γ rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio frequency waves, α rays, β rays, electron beams, plasma flow, ionizing radiation, particle beams, and the like. Preferably it is ultraviolet light.

The light transmittance of the adhesive sheet of the present invention at a wavelength of 500 nm is preferably 70% to 100%, more preferably 75% to 98%, and still more preferably 80% to 95%. If it is in such a range, an adhesive sheet can be obtained which can be well recognized as an adherend to be peeled through the adhesive sheet when the adherend is peeled by irradiation with laser light.

The haze value of the adhesive sheet of the present invention is preferably 70% or less, more preferably 65% or less, and still more preferably 50% or less. If it is in such a range, an adhesive sheet can be obtained which can be well recognized as an adherend to be peeled through the adhesive sheet when the adherend is peeled by irradiation with laser light. The lower the haze value of the adhesive sheet, the better, and the lower limit is, for example, 0.1% (preferably 0%).

When the adhesive layer of the adhesive sheet of the present invention is attached to a stainless steel plate, the initial adhesive force at 23°C is preferably 0.3 N/20 mm～15 N/20 mm, more preferably 0.5 N/20 mm～10 N/20 mm. If it is in this range, an adhesive sheet that can hold the adherend well can be obtained. In addition, an adhesive sheet can be obtained that can exhibit releasability by irradiation with low-energy laser light, has less paste residue, and has excellent directivity during peeling. In this specification, the adhesive force is measured in accordance with JIS (Japanese Industrial Standards) Z 0237:2000. Specifically, the adhesive sheet is attached to the adherend (for example, a stainless steel plate (arithmetic average surface roughness Ra: 40±25 nm)) using a 2 kg roller with 1 round trip, and placed at 23°C for 30 Minutes later, under the conditions of a peeling angle of 180° and a peeling speed (stretching speed) of 300 mm/min, the adhesive sheet was peeled off and measured. The adhesive force of the adhesive layer will change due to the irradiation of active energy rays and laser light. In this specification, the so-called "initial adhesive force" refers to the adhesive force before the active energy rays and laser light are irradiated.

In one embodiment, the adhesive layer of the adhesive sheet is attached to the stainless steel plate and irradiated with 460 mJ/cm ² of ultraviolet light. The adhesive force at 23°C is preferably 0.005 N/20 mm～2.4 N/20 mm , More preferably 0.01 N/20 mm～1.5 N/20 mm, still more preferably 0.02 N/20 mm～1 N/20 mm. If it is such a range, an adhesive sheet with good peelability can be obtained. The above-mentioned ultraviolet irradiation uses, for example, an ultraviolet irradiation device (manufactured by Nitto Seiki Co., Ltd., trade name "UM-810") to irradiate the adhesive layer with ultraviolet light from a high-pressure mercury lamp (characteristic wavelength: 365 nm, cumulative light quantity: 460 mJ/cm ² , irradiation energy : 70 W/cm ² , irradiation time: 6.6 seconds).

After attaching the adhesive layer of the adhesive sheet to the stainless steel plate and irradiating 460 mJ/cm ² of ultraviolet rays, the adhesive force at 23°C relative to the initial adhesive force is preferably 50% or less, and more preferably 40% or less, It is particularly preferably 30% or less, and most preferably 20% or less. If it is such a range, it is possible to obtain an adhesive sheet having particularly excellent releasability and less paste residue after peeling.

The thickness of the adhesive sheet is preferably 1 μm to 300 μm, more preferably 5 μm to 200 μm.

In one embodiment, the above-mentioned adhesive sheet is used as a carrier sheet for an adherend (for example, an electronic component). The adhesive sheet can be used, for example, in the following ways: (1) transfer a plurality of ultra-small parts arranged on other fixing materials onto the adhesive sheet and receive it, (2) irradiate the adhesive sheet with ultraviolet light (for example, , Ultraviolet light with a wavelength of 350 nm ~ 380 nm) to harden the gas generating layer (preferably to harden the entire gas generating layer) to reduce the adhesion, (3) after that, irradiate UV laser light (for example, UV with a wavelength of 355 nm) Laser light), and selectively peel off the ultra-small parts located in the required parts.

As described above, the adhesive sheet of the present invention exhibits good releasability when irradiated with laser light. Here, the so-called good peelability means that (1) it can be peeled with low energy, (2) the paste remains less, and (3) the directivity at the time of peeling is excellent. If it can be peeled off with low energy, it can prevent the deterioration of the part irradiated by laser light. If the paste remains less, it can prevent undesirable situations in subsequent steps. If the directivity during peeling is excellent, it can prevent unnecessary wafers from flying out.

B. Adhesive layer The thickness of the adhesive layer is preferably 0.1 μm to 500 μm, more preferably 3 μm to 100 μm, still more preferably 5 μm to 80 μm, further preferably 5 μm to 50 μm, particularly preferably It is 5 μm～30 μm, the best is 5 μm～20 μm. By reducing the thickness of the adhesive layer within this range, the laser power during peeling can be further reduced, and an adhesive sheet with excellent peeling performance can be obtained. By making the thickness of the adhesive layer 15 μm or more, it is easy to obtain a convex adhesive sheet. By making the thickness of the adhesive layer less than 15 μm, it is easy to obtain a concave adhesive sheet.

As described above, the adhesive layer contains an active energy ray-curable adhesive. In one embodiment, the adhesive layer further contains an ultraviolet absorber.

In one embodiment, the adhesive layer is cured by irradiating ultraviolet rays of 350 nm or more and 380 nm or less (preferably 360 nm or more and 370 nm or less). Whether it has been hardened can be judged by the decrease in adhesive force at 23°C. For example, the adhesive strength of the adhesive layer at 23°C will decrease by 50% to 90% due to hardening.

(Active energy ray hardening adhesive) In one embodiment, as an active energy ray curing adhesive, an active energy ray reactive compound (monomer or oligomer) containing a base polymer that becomes a master agent and an active energy ray reactive compound (monomer or oligomer) that can be bonded to the base polymer is used Energy ray hardening adhesive (A1). In another embodiment, an active energy ray curable adhesive (A2) containing an active energy ray reactive polymer as a base polymer is used. It is preferable that the above-mentioned base polymer has a functional group that can react with a photopolymerization initiator. As this functional group, a hydroxyl group, a carboxyl group, etc. are mentioned, for example.

As the base polymer used in the above-mentioned adhesive (A1), for example, natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber , Recycled rubber, butyl rubber, polyisobutylene rubber, nitrile rubber (NBR (Nitrile Butadiene Rubber, nitrile rubber)) and other rubber-based polymers; silicone-based polymers; acrylic polymers, etc. These polymers can be used individually or in combination of 2 or more types. Among them, acrylic polymers are preferred.

Examples of acrylic polymers include homopolymerization of (meth)acrylates containing hydrocarbon groups such as alkyl (meth)acrylates, cycloalkyl (meth)acrylates, and aryl (meth)acrylates. Compounds or copolymers; copolymers of the hydrocarbon group-containing (meth)acrylate and other copolymerizable monomers. Examples of alkyl (meth)acrylates include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, and tertiary butyl (meth)acrylate. , Pentyl ester, isoamyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, lauryl ester Lauryl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, octadecyl ester, and eicosyl ester. As cycloalkyl (meth)acrylate, cyclopentyl and cyclohexyl (meth)acrylate can be mentioned, for example. The aryl (meth)acrylate may, for example, be phenyl (meth)acrylate and benzyl (meth)acrylate. The content ratio of the structural unit derived from the above-mentioned hydrocarbon group-containing (meth)acrylate is preferably 40 parts by weight or more, more preferably 60 parts by weight or more with respect to 100 parts by weight of the base polymer.

Examples of the above-mentioned other copolymerizable monomers include: carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers Monomers containing functional groups such as acrylamide, acrylamide, and acrylonitrile. As the carboxyl group-containing monomer, for example, acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumarate Acid, and crotonic acid. As an acid anhydride monomer, maleic anhydride and itaconic anhydride are mentioned, for example. Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethyl)acrylate Cyclohexyl) methyl ester. As the glycidyl group-containing monomer, for example, glycidyl (meth)acrylate and glycidyl (meth)acrylate may be mentioned. As the sulfonic acid group-containing monomer, for example, styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide Propanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloxynaphthalenesulfonic acid. As the phosphoric acid group-containing monomer, for example, 2-hydroxyethyl allyl phosphate may be mentioned. The acrylamide may, for example, be N-acryloyl 𠰌line. These may be used individually by 1 type, and may be used in combination of 2 or more types. The content ratio of the structural unit derived from the above-mentioned copolymerizable monomer is preferably 60 parts by weight or less, and more preferably 40 parts by weight or less with respect to 100 parts by weight of the base polymer.

In order to form a crosslinked structure in the polymer backbone of the acrylic polymer, it may contain a structural unit derived from a multifunctional monomer. As the polyfunctional monomer, for example, hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, new Pentylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester, epoxy (meth)acrylate (ie, polyglycidyl (meth)acrylate), polyester (meth)acrylate, and (meth)acrylate urethane. These may be used individually by 1 type, and may be used in combination of 2 or more types. The content ratio of the structural unit derived from the above-mentioned polyfunctional monomer is preferably 40 parts by weight or less, and more preferably 30 parts by weight or less with respect to 100 parts by weight of the base polymer.

The weight average molecular weight of the acrylic polymer is preferably 100,000 to 3 million, more preferably 200,000 to 2 million. The weight average molecular weight can be measured by GPC (gel permeation chromatography) (solvent: THF (Tetrahydrofuran)).

As the above-mentioned active energy ray reactive compound that can be used in the above-mentioned adhesive (A1), for example, a polymerizable carbon-carbon containing acryloyl group, methacryloyl group, vinyl group, allyl group, and ethynyl group can be mentioned. Photoreactive monomers or oligomers of functional groups of multiple bonds. Specific examples of the photoreactive monomer include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6- Esterification products of (meth)acrylic acid and polyhydric alcohols such as hexanediol di(meth)acrylate and polyethylene glycol di(meth)acrylate; multifunctional (meth)acrylate urethane; epoxy (Meth)acrylate; oligoester (meth)acrylate, etc. In addition, methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate), m-isocyanoisopropenyl-α,α- Monomers such as dimethyl benzyl ester. Specific examples of photoreactive oligomers include dimers to pentamers of the above-mentioned monomers, and the like. The molecular weight of the photoreactive oligomer is preferably 100-3000.

In addition, as the active energy ray reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinyl silicone; or oligomers composed of such monomers can be used.

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

In the above-mentioned adhesive (A1), the content ratio of the active energy ray reactive compound relative to 100 parts by weight of the base polymer is preferably 0.1 parts by weight to 500 parts by weight, more preferably 5 parts by weight to 300 parts by weight, and further Preferably it is 40 parts by weight to 150 parts by weight.

As the active energy ray-reactive polymer (base polymer) contained in the above-mentioned adhesive (A2), for example, an acrylic acid group, a methacrylic acid group, a vinyl group, an allyl group, an ethynyl group, etc. A polymer of functional groups of carbon-carbon multiple bonds. Specific examples of active energy ray reactive polymers include: polymers containing polyfunctional (meth)acrylates; photocationic polymerizable polymers; polymers containing cinnamyl groups such as polyvinyl cinnamate; Diazotized amino novolac resin; polypropylene amide, etc.

In one embodiment, the following active energy ray reactive polymer is used, which is formed by introducing active energy ray polymerizable carbon-carbon multiple bonds into the side chain, main chain, and/or main chain end of the above-mentioned acrylic polymer By. As a method of introducing radiation polymerizable carbon-carbon double bonds into acrylic polymers, for example, the following method can be exemplified: raw material monomers containing monomers having specific functional groups (first functional groups) are copolymerized to obtain acrylic After the polymer is polymerized, a compound with a specific functional group (the second functional group) that can react with the first functional group to bond with the radiation polymerizable carbon-carbon double bond is used to maintain the radiation of the carbon-carbon double bond Condensation reaction or addition reaction to acrylic polymer in a polymerizable state.

As the combination of the first functional group and the second functional group, for example, a carboxyl group and an epoxy group, an epoxy group and a carboxyl group, a carboxyl group and an aziridinyl group, an aziridinyl group and a carboxyl group, a hydroxyl group and an isocyanate group may be mentioned. , Isocyanate and hydroxyl. Among these combinations, from the viewpoint of ease of reaction tracking, a combination of a hydroxyl group and an isocyanate group, or a combination of an isocyanate group and a hydroxyl group is preferred. In addition, it is more technically difficult to produce a polymer with a higher reactive isocyanate group. From the viewpoint of the ease of production or acquisition of acrylic polymer, the above-mentioned first on the acrylic polymer side is more preferable. When the 1 functional group is a hydroxyl group, and the above-mentioned second functional group is an isocyanate group. In this case, as an isocyanate compound having both a radiation polymerizable carbon-carbon double bond and an isocyanate group as the second functional group, for example, methacryloyl isocyanate, 2-methyl isocyanate Acrylic oxyethyl, and isopropenyl-α,α-dimethylbenzyl isocyanate. Furthermore, as the acrylic polymer having the first functional group, it is preferable to include a structural unit derived from the above-mentioned hydroxyl-containing monomer, including 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, The structural unit of ether compounds such as diethylene glycol monovinyl ether is also preferable.

The adhesive (A2) may further contain the active energy ray reactive compound (monomer or oligomer).

The active energy ray-curable adhesive may contain a photopolymerization initiator.

、2-氯9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、異丙基9-氧硫𠮿

、2,4-二氯9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

等9-氧硫𠮿

系化合物；樟腦醌；鹵代酮；醯基膦氧化物；醯基膦酸鹽等。光聚合起始劑之使用量可設定為任意適當之量。As the photopolymerization initiator, any appropriate initiator can be used. As the photopolymerization initiator, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethyl styrene Alpha-ketone compounds such as ketone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexylphenylketone, etc.; methoxyacetophenone, 2,2-dimethoxy-2-phenylbenzene Acetophenone compounds such as ethyl ketone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-𠰌linylpropane-1; Benzoin ether, benzoin isopropyl ether, anisin methyl ether and other benzoin ether compounds; ketal compounds such as benzil dimethyl ketal; 2-naphthalenesulfonyl chloride and other aromatic sulfonyl chloride compounds; 1 -Phenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime and other photoactive oxime compounds; benzophenone, benzoic acid, 3,3'-dimethyl-4 -Benzophenone compounds such as methoxybenzophenone; 9-oxysulfur 𠮿

, 2-chloro-9-oxysulfur 𠮿

, 2-Methyl 9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, Isopropyl 9-oxysulfur 𠮿

, 2,4-Dichloro 9-oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

Wait 9-oxysulfur 𠮿

Series compounds; camphorquinone; halogenated ketones; phosphine oxides; phosphonates, etc. The use amount of the photopolymerization initiator can be set to any appropriate amount.

In one embodiment, the absorbance coefficient with a wavelength of 365 nm is 10 ml/g·cm～10000 ml/g·cm (preferably 80 ml/g·cm～8000 ml/g·cm, more preferably 100 ml /g·cm～5000 ml/g·cm) photopolymerization initiator. In the present invention, the adhesive layer is formed so that the light transmittance of the adhesive sheet at a wavelength of 360 nm becomes 0% to 35%. Therefore, light with higher reactivity in the medium wave (for example, 360 nm to 380 nm) region can be used. Polymerization initiator. The adhesive layer containing such a photopolymerization initiator is advantageous in that it is difficult to change the characteristics under conditions that do not need to be cured, such as during storage or use under a UV cut-off lamp. Furthermore, in this specification, the absorbance coefficient refers to the absorbance coefficient in methanol. The method of measuring the absorbance coefficient is described later.

In one embodiment, the absorption coefficient of the photopolymerization initiator at a wavelength of 405 nm is 10 ml/g·cm or less, more preferably 5 ml/g·cm or less.

As the above-mentioned photopolymerization initiator, a commercially available product may also be used. For example, as a photopolymerization initiator with the above-mentioned absorption coefficient characteristics, examples include: "Irgacure 651", "Irgacure 184", "Irgacure 1173", "Irgacure 500", and "Irgacure 2959" manufactured by BASF Corporation. ", "Irgacure 127", "Irgacure 754", "Irgacure MBF", "Irgacure 907", etc.

The content ratio of the photopolymerization initiator is preferably 0.5 parts by weight to 10 parts by weight, and more preferably 1 part by weight to 8 parts by weight with respect to 100 parts by weight of the base polymer of the adhesive.

It is preferable that the said active energy ray hardening type adhesive contains a crosslinking agent. As the crosslinking agent, for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an azoline-based crosslinking agent, an aziridine-based crosslinking agent, a melamine-based crosslinking agent, and a peroxide-based crosslinking agent may be mentioned. Linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents, carbodiimide-based cross-linking agents, amine-based cross-linking agents, etc. .

Relative to 100 parts by weight of the base polymer of the adhesive, the content ratio of the crosslinking agent is preferably 0.5 parts by weight to 10 parts by weight, more preferably 1 part by weight to 8 parts by weight.

In one embodiment, an isocyanate-based crosslinking agent is preferably used. The isocyanate-based crosslinking agent is preferable in that it can react with a variety of functional groups. Specific examples of the above-mentioned isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophoride Alicyclic isocyanates such as ketone diisocyanate; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane/toluene diisocyanate Isocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "Coronate L") Coronate HL"), isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "Coronate HX") and other isocyanate adducts. It is preferable to use a crosslinking agent having 3 or more isocyanate groups.

The active energy ray hardening adhesive may further contain any appropriate additives as needed. Examples of additives include active energy ray polymerization accelerators, radical scavengers, adhesion-imparting agents, and plasticizers (for example, trimellitate-based plasticizers, pyromellitic acid-based plasticizers). Etc.), pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, peeling regulators, softeners, surfactants, flame retardants, antioxidants, etc.

(Ultraviolet absorber) As the ultraviolet absorber, any suitable ultraviolet absorber can be used as long as it is a compound that absorbs ultraviolet light (for example, a wavelength of 355 nm or less). As the ultraviolet absorber, for example, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a tris-based ultraviolet absorber, a salicylate-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber may be mentioned. Absorbents, etc. Among them, tris-based ultraviolet absorbers or benzotriazole-based ultraviolet absorbers are preferred, and tris-based ultraviolet absorbers are particularly preferred. Especially when an acrylic adhesive is used as the adhesive A, the three UV absorbers have high compatibility with the base polymer of the acrylic adhesive, so they can be used preferably. The tri-type ultraviolet absorber is more preferably a compound having a hydroxyl group, and more preferably a hydroxyphenyl tri-type compound (hydroxyphenyl tri-type ultraviolet absorber).

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

As a benzotriazole-based ultraviolet absorber (benzotriazole-based compound), for example, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (trade name " TINUVIN PS", manufactured by BASF Corporation), phenylpropionic acid, and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side Chain and linear alkyl) ester compounds (trade name "TINUVIN 384-2", manufactured by BASF Corporation), 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzo Triazol-2-yl)phenyl]octyl propionate and 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate 2-ethylhexyl acid mixture (trade name "TINUVIN 109", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1- Phenylethyl)phenol (trade name "TINUVIN 900", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)- 4-(1,1,3,3-tetramethylbutyl)phenol (trade name "TINUVIN 928", manufactured by BASF), 3-(3-(2H-benzotriazol-2-yl)-5- The reaction product of methyl tert-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 (trade name "TINUVIN 1130", manufactured by BASF), 2-(2H-benzotriazol-2-yl) ) P-cresol (trade name "TINUVIN P", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol (trade name "TINUVIN 234", manufactured by BASF Corporation), 2-[5-chloro-2H-benzotriazol-2-yl]-4-methyl-6-(tertiary butyl)phenol (trade name "TINUVIN 326", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-di-tertiary amylphenol (trade name "TINUVIN 328", manufactured by BASF Corporation), 2 -(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (trade name "TINUVIN 329", manufactured by BASF Corporation), 2,2'- Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (trade name "TINUVIN 360", manufactured by BASF ), 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) methyl propionate and the reaction product of polyethylene glycol 300 (trade name " TINUVIN 213", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (trade name "TINUVIN 571", BASF Company manufacture), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthaliminomethyl)-5-methylphenyl]benzotriazole (trade name "Sumisorb 250", manufactured by Sumitomo Chemical Co., Ltd.), 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole (trade name "SEESORB 703", manufactured by Shipro Kasei), 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimino Methyl)phenol (trade name "SEESORB 706", manufactured by Shipro Kasei), 2-(4-benzyloxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole (Shipro Kasei) Manufactured with the trade name "SEESORB 7012BA"), 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (trade name "KEMISORB 73", Chemipro Kasei Corporation), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tertiary octylphenol] (trade name "Adekastab LA-31", ADEKA shares Co., Ltd.), 2-(2H-benzotriazol-2-yl)p-cresol (trade name "Adekastab LA-32", manufactured by ADEKA Co., Ltd.), 2-(5-chloro-2H-benzo Triazol-2-yl)-6-tert-butyl-4-methylphenol (trade name "Adekastab LA-36", manufactured by ADEKA Co., Ltd.) and the like.

In one embodiment, as the above-mentioned ultraviolet absorber, the following compound is used: the compound has a structure in which three benzene rings are bonded to the three benzene rings, and is directly bonded to one of the high anionic atoms of the three benzene rings. The total number does not reach 6. By using this compound, the following adhesive sheet can be obtained, which can be irradiated with laser light after a wide range of ultraviolet light (for example, ultraviolet light with a wavelength of 350 nm to 380 nm) (preferably the entire surface) is irradiated Shows excellent peelability. In more detail, as described above, by reducing the highly cationic atoms bonded to the conjugated double bond (conjugated electron system) related to the benzene ring, the expansion of the conjugated electron system is suppressed, and the maximum absorption can be achieved. Compounds with shorter wavelengths. Such a compound is difficult to block the wavelength of the ultraviolet rays used for curing, and is preferable as the ultraviolet absorber used in the present invention. As said compound, the brand name "TINUVIN 400" manufactured by BASF Corporation can be mentioned, for example.

The aforementioned ultraviolet absorber may also be a dye or a pigment. Examples of pigments include azo series, phthalocyanine series, anthraquinone series, lake series, perylene series, pyrenone series, quinacridone series, thioindigo series, bis-indolinone series, and isoindolinone series. Series, quinophthalone series and other pigments. Examples of dyes include azo dyes, phthalocyanine dyes, anthraquinone dyes, carbonyl dyes, indigo dyes, quinonimine dyes, methine dyes, quinoline dyes, and nitro dyes.

The molecular weight of the compound constituting the ultraviolet absorber is preferably 100-1500, more preferably 200-1200, and still more preferably 200-1000. If it is in this range, it is possible to obtain an adhesive sheet that can form a better deformed portion by irradiation with laser light.

In one embodiment, the maximum absorption wavelength of the aforementioned ultraviolet absorber is preferably 350 nm or less, more preferably 340 nm or less. If such an ultraviolet absorber is used, the following adhesive sheet can be obtained, which preferably absorbs ultraviolet rays, can exhibit good peelability, and has excellent characteristic stability under normal conditions.

With respect to 100 parts by weight of the base polymer in the adhesive layer, the content of the ultraviolet absorber is preferably 1 part by weight to 50 parts by weight, more preferably 5 parts by weight to 20 parts by weight. If it is in such a range, an adhesive sheet can be obtained which, when the adhesive force of the entire adhesive layer is reduced well by the irradiation of active energy rays, the curing of the adhesive layer progresses well, and by thunder It shows good peeling performance when irradiated with light.

C. Substrate The aforementioned substrate may contain any appropriate resin. Examples of the resin include polyolefin resins such as polyethylene resins, polypropylene resins, polybutene resins, and polymethylpentene resins, polyurethane resins, and polyester resins. Resins, polyimide resins, polyetherketone resins, polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride resins, fluorine resins, silicon resins, cellulose resins, ion polymerization物resin, etc. Among them, polyolefin resins are preferred.

The thickness of the substrate is preferably 2 μm to 300 μm, more preferably 2 μm to 100 μm, and still more preferably 2 μm to 50 μm.

The light transmittance of the substrate at a wavelength of 355 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more. The upper limit of the light transmittance at 355 nm of the substrate is, for example, 98% (preferably 99%).

D. Other adhesive layer As the adhesive constituting the above-mentioned other adhesive layer, any suitable adhesive can be used as long as the effect of the present invention is obtained. Examples of the above-mentioned adhesives include: acrylic adhesives, silicone adhesives, vinyl alkyl ether adhesives, polyester adhesives, polyamide adhesives, urethane adhesives Adhesives, fluorine-based adhesives, styrene-diene block copolymer-based adhesives, active energy ray-curable adhesives, etc. Among them, acrylic adhesives, rubber adhesives or silicone adhesives are preferred, and acrylic adhesives are more preferred.

When the other adhesive layer of the above-mentioned adhesive sheet is attached to the polyethylene terephthalate film, the adhesive force at 23°C is preferably 0.01 N/20 mm～15 N/20 mm, more preferably 0.05 N /20 mm～10 N/20 mm.

The light transmittance of the above-mentioned other adhesive layer at a wavelength of 355 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more. The upper limit of the light transmittance of the above-mentioned other adhesive layer at a wavelength of 355 nm is, for example, 98% (preferably 99%).

E. Manufacturing method of adhesive sheet The above-mentioned adhesive sheet can be manufactured by any appropriate method. The adhesive sheet can be obtained by coating the above-mentioned adhesive on a substrate or a release liner, for example. As the coating method, can be used: bar coater coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, die lip coating, die nozzle coating, dip coating, Various methods such as offset printing, flexographic printing, and screen printing. In addition, a method of attaching the adhesive layer to the base material after forming the adhesive layer separately on the release liner may also be adopted.

F. Use method of adhesive sheet ( processing method of electronic parts ) The adhesive sheet of the present invention can be used in situations where the processed member is temporarily fixed when the processed member (for example, electronic part) is processed. Taking the processing method of electronic parts as an example, the method of using the adhesive sheet of the present invention will be described. The processing method of the above-mentioned electronic parts can be, for example, the following methods: (i) attaching the electronic part to the adhesive layer of the adhesive sheet and fixing it, (ii) processing the electronic part, (iii) treating the adhesive sheet The entire adhesive layer is irradiated with active energy rays (for example, ultraviolet rays) to reduce the adhesive force of the adhesive sheet. (iv) Laser light is irradiated to the part that needs to be peeled to peel off the electronic parts for use. According to this method, the electronic component can be naturally dropped and peeled off. In addition, when a plurality of electronic components are temporarily fixed, only a part of them may be peeled off. If the adhesive sheet of the present invention is used, the adhesive force can be reduced to the level of natural fall. Therefore, even very small (for example, 50 μm square) electronic parts can be peeled off one by one.

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

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

The size of the above-mentioned electronic component (the area of the attachment surface) is, for example, 1 μm ² to 250,000 μm ² . In one embodiment, the size of the electronic component (the area of the attachment surface) is 1 μm ² to 6400 μm ² for processing. In other embodiments, the size of the electronic component (the area of the attachment surface) is 1 μm ² to 2500 μm ² for processing.

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

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

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

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

(1) Initial adhesion (adhesive layer), adhesion of other adhesive layers Attach the adhesive layer of the adhesive sheet to SUS430, and measure by following the method of JIS Z 0237:2000 (lamination condition: 2 kg roller 1 round trip, stretching speed: 300 mm/min, peeling angle 180°, measuring Temperature: 23°C) to measure the initial adhesion of the adhesive sheet. Furthermore, when the initial adhesive force is 2 N/20 mm or more, it is evaluated that the receptivity (transferability) during transfer of the adherend is remarkably excellent (square in the table); at 0.5 N/20 mm or more and When it is less than 2 N/20 mm, it is evaluated that the transferability (transferability) of the adherend is good (△ in the table); when it is less than 0.5 N/20 mm, it is evaluated as being adhered The receptivity (transferability) during body transfer is insufficient (× in the table). In addition, the adhesive layer of the adhesive sheet is attached and fixed to a support such as a stainless steel plate, and the other adhesive layer is attached to a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror S10", Thickness: 25 μm), measured by the method in accordance with JIS Z 0237: 2000 (bonding conditions: 2 kg roll 1 round trip, stretching speed: 300 mm/min, peeling angle 180°, measurement temperature: 23°C) Adhesion of other adhesive layers.

(2) Adhesive force after UV irradiation: Attach the adhesive layer of the adhesive sheet to SUS430. For the entire surface of the adhesive layer, use an ultraviolet irradiation device (manufactured by Nitto Seiki, trade name "UM-810"). Irradiate high-pressure mercury lamp with ultraviolet light (specific wavelength: 365 nm, cumulative light quantity: 460 mJ/cm ² ). Furthermore, when the adhesive force after ultraviolet irradiation is 0.5 N/20 mm or less, it is evaluated that the peelability is remarkably excellent (square in the table); when it is 0.5 N/20 mm or more and less than 2 N/20 mm In the case, the peelability is evaluated as good (△ in the table); in the case of 2 N/20 mm or more, the peelability is evaluated as insufficient (× in the table).

(3) Light transmittance Set the adhesive sheet on a spectrophotometer (trade name "UV-VIS UV-Visible Spectrophotometer SolidSpec3700", manufactured by Shimadzu Corporation), let the incident light enter perpendicularly to the adhesive layer side of the sample, and measure 300 nm to 800 nm The transmittance of the wavelength region. The transmittance at the wavelengths of 360 nm, 380 nm and 500 nm of the selected transmission spectrum.

(4) Surface shape change of the adhesive sheet. For the entire surface of the adhesive layer of the adhesive sheet, use an ultraviolet irradiation device (manufactured by Nitto Seiki, trade name "UM-810") to irradiate the entire surface with high-pressure mercury lamp ultraviolet light (specific wavelength) : 365 nm, cumulative light intensity: 460 mJ/cm ² ). After that, a glass plate (manufactured by Matsuba Glass Co., Ltd., large glass slide S9112 (standard large white edging No. 2)) was bonded to the adhesive layer to obtain a measurement sample. From the side of the glass plate of the measurement sample, a UV laser with a wavelength of 355 nm and a beam diameter of about 20 μmϕ was used to perform pulse scanning with a power of 0.80 mW and a frequency of 40 kHz, and gas was generated from the adhesive layer. Observe the changes in the shape of the surface of the adhesive sheet produced by this operation.

(5) Haze value Using a haze meter (trade name "HAZE METER HM-150", manufactured by Murakami Color Technology Research Institute), the haze value of the adhesive sheet was measured.

(6) 10% weight reduction temperature Regarding the ultraviolet absorber, the 10% weight reduction temperature is measured. Using a differential thermal analysis device (manufactured by TA Instruments, trade name "Discovery TGA"), at a temperature rise of 10°C/min and a N ₂ atmosphere, the flow rate is set to 25 ml/min, and the weight of the adhesive sheet is reduced by 10%.的温度。 The temperature.

[Production Example 1] Production of acrylic polymer I After adding 100 parts by weight of 2-ethylhexyl acrylate, 12.6 parts by weight of 2-hydroxyethyl acrylate, and 0.25 parts by weight of benzoyl peroxide as a polymerization initiator to toluene, it was carried out at 60°C under a nitrogen stream. In the polymerization reaction, 13.5 parts of methacryloxyethyl isocyanate was added thereto to perform an addition reaction, thereby obtaining a toluene solution of an acrylic copolymer having a carbon-carbon double bond (acrylic polymer I).

[Production Example 2] Production of Acrylic Polymer II To toluene was added 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of ethyl acrylate, 4 parts by weight of 2-hydroxyethyl acrylate, 5 parts by weight of methyl methacrylate, and peroxide as a polymerization initiator After 0.2 parts by weight of benzoyl, it was heated to 70°C to obtain a toluene solution of acrylic copolymer (acrylic polymer II).

[Production Example 3] Production of acrylic polymer a After adding 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, and 0.15 parts by weight of benzoyl peroxide as a polymerization initiator to ethyl acetate, it was heated to 70°C to obtain an acrylic copolymer ( Acrylic polymer a) in ethyl acetate.

[Production Example 4] Production of acrylic polymer b To toluene was added 30 parts by weight of 2-ethylhexyl acrylate, 70 parts by weight of ethyl acrylate, 4 parts by weight of 2-hydroxyethyl acrylate, 5 parts by weight of methyl methacrylate, and peroxide as a polymerization initiator After 0.2 parts by weight of benzoyl, it was heated to 70°C to obtain a toluene solution of acrylic copolymer (acrylic polymer b).

[Example 1] (Preparation of adhesive (1)) To acrylic polymer solution I containing 100 parts by weight of acrylic polymer I, a crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L") 0.2 parts by weight, α-hydroxyketone-based photopolymerization initiator (manufactured by BASF Japan, trade name "Irgacure 127", molecular weight: 340.4, absorbance coefficient at 365 nm: 1.07×10 ² ml/g·cm) 3 parts by weight, 20 parts by weight of hydroxyphenyl tris-based ultraviolet absorber (manufactured by BASF Japan, trade name "Tinuvin 400", molecular weight: 647.8, 10% weight reduction temperature: 391.7°C, maximum absorption wavelength: 336 nm) Adhesive (1). (Preparation of Adhesive (2)) To the ethyl acetate solution of acrylic polymer a containing 100 parts by weight of acrylic polymer a, a crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C") ) 2 parts by weight to obtain the adhesive (2). (Adhesive sheet) On one side of a polyethylene terephthalate film (thickness: 50 μm), the adhesive (1) is applied so that the thickness after the solvent volatilizes (drying) becomes 10 μm to form an adhesive layer, On the other side, the adhesive (2) is applied so that the thickness after the solvent volatilizes (drying) becomes 10 μm to form another adhesive layer, thereby obtaining an adhesive sheet. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (6). The results are shown in Table 1.

[Examples 2-13, Comparative Examples 1-7] The type of acrylic polymer, the amount of cross-linking agent, the type of photopolymerization initiator, the amount of blending, the type of ultraviolet absorber, the amount of blending, and the adhesive layer The thickness is as shown in Table 1 and Table 2, except that the adhesive sheet was obtained in the same manner as in Example 1. The obtained adhesive sheet was used for the above-mentioned evaluations (1) to (6). The results are shown in Table 1 or Table 2. Furthermore, in Comparative Example 1, 20 parts by weight of a surfactant (manufactured by Kao Corporation, trade name "EXCEPARL IPP") was also added to the adhesive. In Example 13, the adhesive (curing adhesive) was applied to only one side. In Comparative Example 4, 10 parts by weight of terpene phenol-based adhesion-imparting resin (manufactured by Yasuhara Chemical Co., Ltd., trade name "YS POLYSTER S145") was added to the adhesive. The contents of the materials listed in Table 1 are as follows. "Irg 651": manufactured by BASF Japan, brand name "Irgacure 651", molecular weight: 256.3, absorbance coefficient at 365 nm wavelength: 3.613×10 ² ml/g·cm "Tinuvin 477": manufactured by BASF Japan, brand name "Tinuvin 477", molecular weight: 958.2, 10% weight reduction temperature: 352.8°C, maximum absorption wavelength: 356 nm)

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Adhesive layer composition polymer Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Crosslinking agent Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Crosslinking agent blending amount [parts by weight] 0.2 1 1 1 1 1 1 Photopolymerization initiator Irg127 Irg127 Irg127 Irg127 Irg127 Irg127 Irg127 Preparation amount of photopolymerization initiator [parts by weight] 3 3 3 3 3 3 3 UV absorber Tinuvin400 Tinuvin400 Tinuvin400 Tinuvin400 Tinuvin400 Tinuvin400 Tinuvin400 Blending amount of ultraviolet absorber [parts by weight] 20 20 20 20 20 20 10 Thickness [μm] 10 5 10 15 20 30 5 Substrate layer Material PET PET PET PET PET PET PET Thickness [μm] 50 50 50 50 50 50 50 Other adhesive layer composition polymer Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer a Crosslinking agent Tetrad C Tetrad C Tetrad C Tetrad C Tetrad C Tetrad C Tetrad C Crosslinking agent blending amount [parts by weight] 2 2 2 2 2 2 2 Thickness [μm] 10 10 10 10 10 10 10 Evaluation Initial adhesion (adhesive layer) [N/20 mm] 8.37 2.43 3.15 4.20 4.53 6.15 0.77 Adhesion after UV irradiation [N/20 mm] 0.06 0.07 0.13 0.21 0.65 1.20 0.05 Change rate of adhesion 0.7% 2.7% 4.2% 5.1% 14.4% 19.5% 6.0% Adhesive force of other adhesive layer [N/20 mm] 0.71 0.71 0.73 0.74 0.78 0.78 0.73 Transmittance Transmittance @360 nm[%] 1.10 4.94 1.06 0.42 0.22 0.02 15.91 Transmittance @380 nm[%] 56.63 68.30 57.04 49.63 42.44 31.24 77.73 Transmittance @500 nm[%] 89.81 91.71 91.70 91.69 91.66 91.65 91.89 Surface shape change State (convex foam...bubbles and not broken under the microscope) (concave broken...vaporized and sunken) Rupture Rupture Rupture Foam convex Foam convex Foam convex Rupture Haze [%] 2.1 2 2.4 2.6 2.5 2.7 2.2 Transferability 〇 〇 〇 〇 〇 〇 △ Peelability 〇 〇 〇 〇 △ △ 〇 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Adhesive layer composition polymer Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Crosslinking agent Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Crosslinking agent blending amount [parts by weight] 1 1 1 1 1 1 Photopolymerization initiator Irg127 Irg127 Irg127 Irg127 Irg127 Irg651 Preparation amount of photopolymerization initiator [parts by weight] 3 3 3 3 3 3 UV absorber Tinuvin400 Tinuvin400 Tinuvin400 Tinuvin400 Tinuvin400 Tinuvin400 Blending amount of ultraviolet absorber [parts by weight] 10 10 5 5 5 20 Thickness [μm] 20 30 5 20 50 10 Substrate layer Material PET PET PET PET PET PET Thickness [μm] 50 50 50 50 50 50 Other adhesive layer composition polymer Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer a - Crosslinking agent Tetrad C Tetrad C Tetrad C Tetrad C Tetrad C - Crosslinking agent blending amount [parts by weight] 2 2 2 2 2 - Thickness [μm] 10 10 10 10 10 - Evaluation Initial adhesion (adhesive layer) [N/20 mm] 2.62 3.53 0.80 1.60 3.08 3.15 Adhesion after UV irradiation [N/20 mm] 0.10 0.15 0.04 0.06 0.13 0.10 Change rate of adhesion 3.7% 4.3% 5.2% 3.8% 4.2% 3.3% Transmittance Transmittance @360 nm[%] 1.20 0.21 33.52 7.09 0.39 0.90 Transmittance @380 nm[%] 58.85 49.19 83.12 72.00 55.25 53.04 Transmittance @500 nm[%] 91.72 91.66 91.94 91.80 91.56 91.11 Surface shape change State (convex foam...bubbles and not broken under the microscope) (concave broken...vaporized and sunken) Foam convex Foam convex Rupture Foam convex Foam convex Rupture Haze [%] 2.5 2.4 2.3 2.3 2.9 2.5 Transferability 〇 〇 △ △ 〇 〇 Peelability 〇 〇 〇 〇 〇 〇

[Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Adhesive layer composition polymer Acrylic Polymer II Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Acrylic Polymer I Crosslinking agent Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Coronate/L Crosslinking agent blending amount [parts by weight] 3 0.2 0.2 1 0.2 1 1.5 Photopolymerization initiator - Irg127 Irg651 Irg127 Irg127 Irg127 Irg127 Preparation amount of photopolymerization initiator [parts by weight] - 3 3 3 3 3 3 UV absorber Tinuvin477 Tinuvin477 Tinuvin477 - - - - Blending amount of ultraviolet absorber [parts by weight] 20 20 20 - - - - Thickness [μm] 7 5 5 20 30 5 5 Substrate layer Material PET PET PET PET PET PET PET Thickness [μm] 50 50 50 50 50 50 50 Other adhesive layer composition polymer Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer a Acrylic polymer b Acrylic polymer b Acrylic polymer b Crosslinking agent Tetrad C Tetrad C Tetrad C Tetrad C Coronate/L Coronate/L Coronate/L Crosslinking agent blending amount [parts by weight] 2 2 2 2 1 1 1 Thickness [μm] 10 10 10 10 10 10 10 Evaluation Initial adhesion (adhesive layer) [N/20 mm] 0.48 4.58 4.58 5.20 7.88 0.56 0.30 Adhesion after UV irradiation [N/20 mm] 0.48 2.89 2.42 0.08 0.06 0.05 0.05 Change rate of adhesion - 63.1% 52.8% 1.5% 0.8% 8.3% 15.6% Transmittance Transmittance @360 nm[%] 1.34 0.32 0.37 84.06 83.26 84.01 84.10 Transmittance @380 nm[%] 1.98 0.66 0.87 87.15 86.21 87.60 87.39 Transmittance @500 nm[%] 91.35 90.80 91.20 89.86 89.43 90.23 90.45 Surface shape change State (convex foam...bubbles and not broken under the microscope) (concave broken...vaporized and sunken) Rupture Rupture Rupture constant constant constant constant Haze [%] 1.9 2.3 2.2 2.2 2.5 2.1 1.8 Transferability X 〇 〇 〇 〇 △ X Peelability 〇 X X 〇 〇 〇 〇

10: Adhesive layer 20: Substrate 100, 100': Adhesive sheet

Fig. 1(a) is a schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention. Fig. 1(b) is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention.

10: Adhesive layer

20: Substrate

100, 100': Adhesive sheet

Claims (19)

An adhesive sheet, which is provided with an adhesive layer containing an active energy ray hardening adhesive, The light transmittance of the adhesive sheet with a wavelength of 360 nm is 0% to 35%, The light transmittance of the adhesive sheet with a wavelength of 380 nm is 10% to 100%. Such as the adhesive sheet of claim 1, wherein the initial adhesive force at 23°C when the adhesive layer of the adhesive sheet is attached to the stainless steel plate is 0.3 N/20 mm to 15 N/20 mm. Such as the adhesive sheet of claim 1 or 2, in which the adhesive layer of the adhesive sheet is attached to the stainless steel plate and ^{the adhesive force at 23°C after irradiating 460 mJ/cm 2} of ultraviolet rays is 0.01 N/20 mm～2.4 N/20 mm. Such as the adhesive sheet of any one of claims 1 to 3, wherein the adhesive layer of the adhesive sheet is attached to a stainless steel plate and ^{the adhesive force at 23°C after irradiating 460 mJ/cm 2} of ultraviolet light is relative to the initial adhesion The force is less than 50%. For example, the adhesive sheet of any one of claims 1 to 4 has a light transmittance of 70% to 100% at a wavelength of 500 nm. For example, the adhesive sheet of any one of claims 1 to 5 has a haze value of 50% or less. The adhesive sheet according to any one of claims 1 to 6, wherein the adhesive layer contains an ultraviolet absorber, The maximum absorption wavelength of the ultraviolet absorber is 350 nm or less. The adhesive sheet of claim 7, wherein the above-mentioned ultraviolet absorber is the following compound: the compound has a structure in which three benzene rings are bonded to the three benzene rings, and is directly bonded to the three benzene rings with high cationicity The total number of atoms does not reach 6. The adhesive sheet according to any one of claims 1 to 8, wherein the adhesive layer contains a photopolymerization initiator, The absorbance coefficient of the photopolymerization initiator at a wavelength of 365 nm is 10 ml/g·cm～10000 ml/g·cm. The adhesive sheet according to any one of claims 1 to 8, wherein the adhesive layer contains a photopolymerization initiator, The light absorption coefficient of the photopolymerization initiator at a wavelength of 405 nm is less than 10 ml/g·cm. The adhesive sheet according to any one of claims 1 to 10, wherein the adhesive layer is cured by irradiating ultraviolet rays of 350 nm or more and 380 nm or less. The adhesive sheet according to any one of claims 1 to 11, wherein the thickness of the adhesive layer is 0.1 μm-50 μm. The adhesive sheet according to any one of claims 1 to 12, wherein the surface of the adhesive sheet is deformed by irradiation with laser light. The adhesive sheet of claim 13, wherein the surface of the adhesive sheet is deformed into a convex shape by irradiation with laser light. The adhesive sheet of claim 13, wherein the surface of the adhesive sheet is deformed into a concave shape by irradiation with laser light. A processing method of electronic parts, which includes: For the adhesive sheet as in any one of Claims 1 to 15, the electronic parts are attached to the adhesive sheet and fixed, Process the electronic parts, The entire adhesive layer of the adhesive sheet is irradiated with active energy rays to reduce the adhesive force of the adhesive sheet, and thereafter, Laser light is irradiated to the part that needs to be peeled, and the electronic parts are peeled off. For example, the processing method of electronic components of claim 16, wherein the above-mentioned peeling of electronic components is performed at selected locations. Such as the processing method of electronic parts in claim 16 or 17, wherein the above-mentioned processing is grinding processing, cutting processing, die bonding, wire bonding, etching, evaporation, molding, circuit formation, inspection, product inspection, cleaning, transfer, Arrangement, repair or device surface protection. For example, the processing method of electronic components in any one of claim 16 to 18, which includes: arranging the electronic components on other sheets after peeling off the electronic components from the adhesive sheet.

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