JP5801010B2 - Adhesive sheet - Google Patents

Description

  The present invention relates to an adhesive sheet.

  In the manufacture of electronic components such as silicon wafers, multilayer capacitors, and transparent electrodes, it is necessary to reduce the size of a substrate obtained by creating necessary functions in a large area to a desired size by cutting. Is called. At the time of cutting, a pressure-sensitive adhesive sheet for fixing a workpiece (substrate) for preventing a reduction in cutting accuracy due to stress and vibration during processing is used. The pressure-sensitive adhesive sheet is required to have a sufficient adhesive force with respect to the workpiece during processing, and after processing, it is required that the cut workpiece (electronic component) can be easily peeled off.

  In recent years, electronic components have become lighter, smaller, and more flexible, resulting in a decrease in yield due to defects during cutting. Specifically, when taking out the workpiece (cut piece) that has been cut from the pressure-sensitive adhesive sheet, defects occur such as chipping on the workpiece end surface, or cracking of the workpiece due to the chipping. There is a problem.

JP 2002-121510 A

  The inventor of the present application has found that the cause of the above problem is that the interval between the cut pieces generated by cutting becomes narrower or disappears after cutting (that is, the cut pieces come into contact or reattach). The present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide a pressure-sensitive adhesive sheet that can prevent the occurrence of problems when cutting a micro component such as an electronic component. More specifically, it is an object of the present invention to provide a pressure-sensitive adhesive sheet that can suppress a decrease in the interval between the cut workpieces.

The pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer and a resin layer disposed on one side of the pressure-sensitive adhesive layer, and a cutting groove is formed from the pressure-sensitive adhesive layer side so as to penetrate the pressure-sensitive adhesive layer. In this case, the cut groove does not disappear after 1 hour at 25 ° C. after the formation of the cut groove.
In preferable embodiment, the thickness of the said adhesive layer is 50 micrometers or less.
In preferable embodiment, the elasticity modulus by the nanoindentation method in 25 degreeC of the said resin layer is 1 Mpa or more.
In a preferred embodiment, the adhesive strength of the pressure-sensitive adhesive sheet of the present invention is reduced by heating.
In preferable embodiment, the said adhesive layer contains a thermally expansible microsphere.
In a preferred embodiment, the pressure-sensitive adhesive sheet of the present invention has a ratio (a2 / a1) of the pressure-sensitive adhesive force (a1) before heating to the pressure-sensitive adhesive force (a2) after heating is 0.0001 to 0.5. .
In a preferred embodiment, the surface roughness Ra of the surface of the pressure-sensitive adhesive layer opposite to the resin layer when the thermally expandable microspheres are expanded or foamed by heating is 3 μm or more.
In preferable embodiment, the adhesive sheet of this invention is further equipped with a base material on the opposite side to the said adhesive layer of the said resin layer.
According to another aspect of the present invention, a method for manufacturing an electronic component is provided. This manufacturing method includes cutting the electronic component material after attaching the electronic component material on the pressure-sensitive adhesive sheet.

  According to the present invention, an electronic component includes an adhesive layer and a resin layer disposed on one side of the adhesive layer, and when the cutting groove is formed, the cutting groove is less likely to narrow with time. It is possible to provide a pressure-sensitive adhesive sheet capable of preventing the occurrence of defects by preventing contact or reattachment of a cut piece when cutting a micropart such as the above.

It is a schematic sectional drawing of the adhesive sheet by preferable embodiment of this invention. (A)-(d) is a schematic sectional drawing which shows typically the cutting groove formed in the adhesive sheet. It is a schematic sectional drawing of the adhesive sheet by one Embodiment of this invention. It is a schematic sectional drawing of the adhesive sheet by another preferable embodiment of this invention. It is a figure which shows the Raman mapping obtained by the measurement of the thickness in Example 3. It is a figure which shows the SEM image of the cross section of the adhesive sheet in Example 11. FIG.

A. 1 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 pressure-sensitive adhesive layer 10 and a resin layer 20 disposed on one side of the pressure-sensitive adhesive layer 10. Although not shown, release paper may be disposed on the pressure-sensitive adhesive layer 10 to protect the pressure-sensitive adhesive layer 10 until the pressure-sensitive adhesive sheet is put to practical use. In the illustrated example, the interface 1 between the pressure-sensitive adhesive layer 10 and the resin layer 20 is clearly illustrated, but the interface may be an interface that is difficult to distinguish visually or with a microscope. The interface that is difficult to discriminate visually or with a microscope can be discriminated by analyzing the composition of each layer, for example (details will be described later).

  Fig.2 (a) is a schematic sectional drawing which shows typically the adhesive sheet of this invention in which the cutting groove was formed. When the adhesive sheet of the present invention is formed from the adhesive layer 10 side so as to penetrate the adhesive layer 10 and the cut groove 2 is formed, after the cut groove 2 is formed, the cut groove 2 Will not disappear. In the present specification, the “cutting groove” refers to a groove formed in the pressure-sensitive adhesive sheet, assuming that the pressure-sensitive adhesive sheet of the present invention is used as a temporary fixing sheet when cutting an electronic component or the like. Say. In one embodiment, the cut groove formed so as to penetrate the pressure-sensitive adhesive layer 10 is a cut groove whose cross-sectional shape in the line width direction is rectangular or trapezoidal in the pressure-sensitive adhesive layer. Any appropriate method can be adopted as a method for forming the cutting groove. Examples thereof include a method of forming using a blade such as a rotary blade and a flat blade, a method of forming using a laser beam, and the like.

  In this specification, “the cutting groove does not disappear” means that the virtual surface A corresponding to the sectional view shape in the line width direction of the cutting groove in the adhesive layer is the area S1 of the virtual surface A immediately after the cutting groove is formed. It means that the ratio (S2 / S1) of the area S2 of the virtual plane A after 1 hour has passed at 25 ° C. after the formation of the cut groove is larger than 0.1. (S2 / S1) is preferably greater than 0.5. In FIG. 2, the virtual plane A is defined by a solid line and dotted lines a and b that define the cross-sectional shape of the cutting groove in the adhesive layer. Moreover, the area of the virtual surface A and the virtual surface B described later can be obtained by, for example, visual observation or cross-sectional observation with a microscope such as SEM. 2B and 2C show an example of a sectional view of the cut groove after the cut groove is formed in the pressure-sensitive adhesive sheet of the present invention and one hour has passed at 25 ° C. FIG. 2D shows an example in which the cutting groove disappears. Preferably, after the cut groove is formed, the depth h of the cut groove in the pressure-sensitive adhesive layer after 1 hour at 25 ° C. is preferably 10% or more with respect to the thickness of the pressure-sensitive adhesive layer, and more preferably It is 50% or more, more preferably 80% or more, and particularly preferably 100%.

  For the virtual surface B corresponding to the sectional view shape in the line width direction of the cut surface in the resin layer, the virtual surface B after 1 hour has elapsed at 25 ° C. after forming the cut groove with respect to the area S3 of the virtual surface B in the cut groove formation The area S4 ratio (S4 / S3) is preferably greater than 0.3, more preferably greater than 0.7.

  The cut groove may not disappear at least partially in the length direction in plan view (the direction perpendicular to the paper surface in FIG. 2). Preferably, the length of the cut groove that has not disappeared after 1 hour at 25 ° C. after the formation of the cut groove is the length of the cut groove immediately after formation (that is, the sum of the cut groove that has not disappeared and the cut groove that has not disappeared). ) Is preferably 10% or more, more preferably 40% or more, further preferably 70% or more, more preferably 80% or more, and particularly preferably 100%.

  According to the present invention, the pressure-sensitive adhesive layer has a slight fluidity even at room temperature, and the cutting groove is narrowed. By appropriately controlling this property, an adhesive sheet in which the cutting groove does not disappear can be obtained. Can do. The adhesive sheet that does not lose the cutting groove prevents the occurrence of defects by preventing contact or reattachment of the work piece (hereinafter also referred to as a cut piece) cut when cutting fine parts such as electronic parts. Can do. Such an adhesive sheet can be obtained, for example, by including the resin layer, appropriately setting the elastic modulus of the resin layer, and reducing the thickness of the resin layer.

  In one embodiment, the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet whose adhesive strength is reduced by heating. FIG. 3 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to one embodiment of the present invention, and shows an example of a pressure-sensitive adhesive sheet whose adhesive strength is reduced by heating. In the pressure-sensitive adhesive sheet 200, the pressure-sensitive adhesive layer 10 includes the thermally expandable microspheres 11. In the pressure-sensitive adhesive sheet 200, the heat-expandable microspheres 11 are present in the pressure-sensitive adhesive layer 10. Therefore, when the adherend (for example, a cut piece) is peeled from the pressure-sensitive adhesive sheet, the heat-expandable microspheres 11 are By heating at a temperature at which expansion or foaming is possible, unevenness is generated on the adhesive surface, and the adhesive force of the adhesive surface can be reduced or eliminated. Practically, the pressure-sensitive adhesive layer 10 further includes a pressure-sensitive adhesive 12. The thermally expandable microsphere 11 may protrude from the pressure-sensitive adhesive layer 10 to the resin layer 20. The thermally expandable microspheres 11 protruding from the pressure-sensitive adhesive layer 10 can be covered with the resin layer 20. As a result, it is possible to eliminate the influence of unevenness due to the thermally expandable microspheres 11 at the time of sticking (that is, before heating).

  FIG. 4 is a schematic cross-sectional view of an adhesive sheet according to another preferred embodiment of the present invention. The pressure-sensitive adhesive sheet 300 further includes a base material 30 on the opposite side of the resin layer 20 from the pressure-sensitive adhesive layer 10. Although not shown, any appropriate other pressure-sensitive adhesive layer or adhesive layer may be provided on the side of the substrate 30 opposite to the resin layer 20. Moreover, the release sheet may be arrange | positioned on the outer side of the base material 30 until the adhesive sheet of this invention is put to practical use. When disposing release paper on the outside of the substrate 30, the release paper can be attached to the substrate via any suitable adhesive. In FIG. 4, although the adhesive layer 10 and the resin layer 20 are formed on one side of the substrate 30, the adhesive layer 10 and the resin layer 20 are formed on both sides of the substrate 30, for example, The composition of adhesive layer / resin layer / base material / resin layer / adhesive layer may be employed.

  As described above, the pressure-sensitive adhesive sheet of the present invention includes a resin layer. In the present invention, the following effects can be obtained by providing the resin layer. That is, first, by providing the resin layer, the thickness of the pressure-sensitive adhesive layer can be reduced while the thickness of the entire pressure-sensitive adhesive sheet is set to a sufficient thickness when cutting. If the thickness of the entire pressure-sensitive adhesive sheet is sufficient, it is possible to prevent the pressure-sensitive adhesive sheet from being completely cut without requiring strict control during cutting of the adherend. Thus, if the risk of completely cutting the adhesive sheet is low, it becomes easy to reach the cutting blade to the adhesive sheet. If the cutting blade reaches the pressure-sensitive adhesive sheet, the distance between the cut pieces immediately after cutting can be increased. On the other hand, if the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet is thin, it is possible to prevent the cut pieces from coming into contact or reattaching over time after cutting. This is considered to be because by reducing the amount of the pressure-sensitive adhesive layer exhibiting fluidity, it is possible to prevent the cutting grooves generated in the pressure-sensitive adhesive layer from being narrowed. Also, if the pressure-sensitive adhesive layer is thin, a pressure-sensitive adhesive sheet that can contribute to the realization of excellent cutting accuracy as a temporary fixing sheet when cutting electronic parts and the like can be obtained. More specifically, if the pressure-sensitive adhesive layer is thin, the pressure-sensitive adhesive sheet is less deformed, so that the cut surface becomes slanted or becomes S-shaped, and chip breakage occurs during cutting. Etc. can be prevented. In addition, when the pressure-sensitive adhesive sheet having a thin pressure-sensitive adhesive layer is used as a temporary fixing sheet when cutting an electronic component or the like, generation of cutting waste can be suppressed. The pressure-sensitive adhesive sheet of the present invention exhibits the above-described effect in cutting with a rotary blade frequently used in a dicing process, and also has the above-described effect in cutting with a flat blade adopted to reduce cutting loss. It is particularly useful. Further, even when cutting under heating (for example, 30 ° C. to 150 ° C.), the cutting can be performed with high accuracy as described above.

  Second, even when the pressure-sensitive adhesive layer includes thermally expandable microspheres as shown in FIG. 3, the resin layer is provided to allow the thermally expandable microspheres to protrude from the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer can be thinned, and the above effects can be obtained. Thus, even when including thermally expandable microspheres, it is one of the achievements of the present invention that an adhesive sheet capable of accurately cutting a workpiece by preventing contact or reattachment of a cut piece can be obtained. is there.

  The pressure-sensitive adhesive force when the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet of the present invention (that is, the surface opposite to the resin layer of the pressure-sensitive adhesive layer) is attached to a polyethylene terephthalate film (for example, a thickness of 25 μm) is preferably 0.2 N / It is 20 mm or more, More preferably, it is 0.2 N / 20 mm-20 N / 20 mm, More preferably, it is 2 N / 20 mm-10 N / 20 mm. If it is such a range, the adhesive sheet useful as a temporary fixing sheet at the time of cutting an electronic component etc. can be obtained. In the present specification, the adhesion is an adhesion measured by a method according to JIS Z 0237: 2000 (measurement temperature: 23 ° C., bonding condition: 2 kg roller 1 reciprocation, peeling speed: 300 mm / min, peeling angle 180 °). I say power.

  When the pressure-sensitive adhesive sheet of the present invention is reduced in adhesive strength by heating, the pressure-sensitive adhesive force after the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet of the present invention is adhered to a polyethylene terephthalate film (for example, thickness 25 μm) and heated is preferably 0.00. It is 2N / 20mm or less, More preferably, it is 0.1N / 20mm or less. In the present specification, the heating of the pressure-sensitive adhesive sheet refers to heating at a temperature and time at which the heat-expandable microspheres expand or foam and the adhesive force is reduced. The heating is, for example, heating at 70 ° C. to 270 ° C. for 1 minute to 10 minutes.

  When the adhesive strength of the pressure-sensitive adhesive sheet of the present invention is reduced by heating, the pressure-sensitive adhesive strength when the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet of the present invention is adhered to a polyethylene terephthalate film (for example, 25 μm thick) (that is, the pressure-sensitive adhesive strength before heating (a1) )) And the adhesive force (a2) after heating (a2 / a1) is preferably 0.5 or less, more preferably 0.1 or less. The lower limit of (a2 / a1) is preferably 0.0001, and more preferably 0.0005.

  When the adhesive strength of the pressure-sensitive adhesive sheet of the present invention decreases due to heating, the pressure-sensitive adhesive sheet is heated at a predetermined temperature as described above, thereby causing unevenness on the pressure-sensitive adhesive surface. The surface roughness Ra of the pressure-sensitive adhesive surface after heating the pressure-sensitive adhesive sheet is preferably 3 μm or more, more preferably 5 μm or more. Within such a range, a pressure-sensitive adhesive sheet can be obtained in which the adhesive strength decreases or disappears after heating and the adherend can be easily peeled off. The surface roughness Ra of the pressure-sensitive adhesive surface refers to the surface roughness Ra of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet after heating without an adherend. The surface roughness Ra can be measured according to JIS B 0601: 1994.

  The thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm to 500 μm. Within such a range, it is possible to prevent the adhesive sheet from being completely cut without requiring strict control at the time of cutting the adherend.

B. Resin layer The elastic modulus of the resin layer by a nanoindentation method at 25 ° C is preferably 1 MPa or more, more preferably 1 MPa to 5000 MPa, still more preferably 1 MPa to 3500 MPa, and particularly preferably 1 MPa to 1000 MPa. Yes, most preferably 50 MPa to 600 MPa. The pressure-sensitive adhesive sheet having a layer exhibiting such an elastic modulus can be obtained, for example, by forming a resin layer formed of a material different from the pressure-sensitive adhesive layer. The modulus of elasticity by the nanoindentation method is obtained by continuously measuring the load and depth of indentation when the indenter is pushed into the sample (for example, adhesive surface) during loading and unloading. The elastic modulus obtained from the applied load-indentation depth curve. In this specification, the elastic modulus by the nanoindentation method means an elastic modulus measured as described above under the measurement conditions of load: 1 mN, load / unloading speed: 0.1 mN / s, and holding time: 1 s.

  By providing a resin layer having an elastic modulus of 1 MPa or more by the nanoindentation method as described above, a cut groove is difficult to disappear, and a pressure-sensitive adhesive sheet that can prevent contact or reattachment of a cut piece during cutting processing is obtained. be able to. Moreover, the adhesive sheet which can contribute to the implementation | achievement of the outstanding cutting precision can be provided. Furthermore, by setting the elastic modulus of the resin layer by the nanoindentation method to 5000 MPa or less, the resin layer impairs necessary flexibility (for example, flexibility enough to follow the adherend) as the entire pressure-sensitive adhesive sheet. It is possible to provide an adhesive sheet that can contribute to the realization of excellent cutting accuracy. Further, damage or deterioration of the cutting blade during cutting processing can be prevented.

  The tensile elastic modulus at 25 ° C. of the resin layer is preferably 1 MPa or more, more preferably 1 MPa to 5000 MPa, and further preferably 1 MPa to 1000 MPa. If it is such a range, the effect similar to the effect demonstrated above about the elasticity modulus by a nanoindentation method can be acquired. The tensile modulus can be measured according to JIS K 7161: 2008.

  The bending elastic modulus at 25 ° C. of the resin layer is preferably 1 MPa or more, more preferably 1 MPa to 5000 MPa, and further preferably 1 MPa to 1000 MPa. If it is such a range, the effect similar to the effect demonstrated above about the elasticity modulus by a nanoindentation method can be acquired. The flexural modulus can be measured according to JIS K 7171: 2008.

  The thickness of the resin layer can be set to any appropriate value. When the pressure-sensitive adhesive layer contains thermally expandable microspheres, the thickness of the resin layer is preferably a thickness that can cover all the thermally expandable microspheres protruding from the pressure-sensitive adhesive layer. The thickness of the resin layer is, for example, 0.1 μm to 200 μm, preferably 0.1 μm to 100 μm, and more preferably 0.1 μm to 45 μm. In this specification, the thickness of the resin layer refers to the distance from the interface between the material constituting the resin layer 20 and the pressure-sensitive adhesive 12 constituting the pressure-sensitive adhesive layer 10 to the surface opposite to the interface of the resin layer. Say distance. That is, in the case where the pressure-sensitive adhesive layer includes thermally expandable microspheres, as shown in FIG. 3, the portion where the thermally expandable microspheres 11 protrude from the pressure-sensitive adhesive layer 10 is the object of evaluation of the thickness of the resin layer. It is outside. In addition, when the adhesive sheet is cleaved and the cut section is visually observed, when the interface between the material constituting the resin layer 20 and the adhesive 12 constituting the adhesive layer 10 is clear, the thickness of the resin layer is It can be measured using a ruler, caliper, micrometer. Moreover, you may measure the thickness of a resin layer using microscopes, such as an electron microscope, an optical microscope, and an atomic force microscope. Further, the thickness of the resin layer may be measured by discriminating the interface based on the difference in composition between the resin layer and the pressure-sensitive adhesive layer. For example, Raman spectroscopy, infrared spectroscopy, X-ray electron spectroscopy, etc .; matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOFMS) and time-of-flight secondary ion mass spectrometer (TOF-SIMS) The composition of the material constituting the resin layer and the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer are analyzed by mass spectrometry and the like, and the thickness of the resin layer can be measured by discriminating the interface based on the difference in the composition. Thus, the method of discriminating the interface by spectroscopic analysis or mass spectrometry is useful when it is difficult to discriminate the interface visually or by observation with a microscope.

  Examples of the material constituting the resin layer include silicone polymers, epoxy polymers, polycarbonate polymers, vinyl polymers, acrylic polymers, urethane polymers, polyester polymers (for example, polyethylene terephthalate), polyolefin polymers, Polymer materials such as polyamide-based polymers, polyimide-based polymers, and unsaturated hydrocarbon-based polymers can be used. If these polymer materials are used, it is possible to easily form a resin layer having the above elastic modulus by appropriately selecting a monomer type, a crosslinking agent, a polymerization degree, and the like. The polymer material is excellent in affinity with the thermally expandable microsphere, the pressure-sensitive adhesive constituting the resin layer, and the base material. You may use said polymer material individually or in combination of 2 or more types.

  As a material constituting the resin layer, a resin material that can be cured (increased elastic modulus) by irradiation with active energy rays may be used. If the resin layer is formed of such a material, the elastic sheet has low elasticity and flexibility and is easy to handle at the time of attaching the adhesive sheet. An adhesive sheet that can be adjusted can be obtained. Examples of the active energy rays include gamma rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio waves, alpha rays, beta rays, electron beams, plasma flows, ionizing rays, particle rays and the like. A resin layer made of a resin material that can be cured by irradiation with active energy rays has an elastic modulus by the nanoindentation method after irradiation of active energy rays within the above range. Moreover, it is preferable that the said tensile elastic modulus and / or bending elastic modulus after irradiation of an active energy ray become the said range for the resin layer comprised from the resin material which can be hardened | cured by irradiation of an active energy ray.

  Examples of resin materials that can be cured (increased elastic modulus) by irradiation with active energy rays include, for example, an ultraviolet curing system (written by Kiyomi Kato, published by General Technology Center, (1989)), photocuring technology (Technical Information Association ( 2000)), JP 2003-292916 A, Patent 4151850, and the like. More specifically, a resin material (R1) containing a polymer as a base material and an active energy ray reactive compound (monomer or oligomer), a resin material (R2) containing an active energy ray reactive polymer, and the like can be mentioned.

  Examples of the base polymer 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 thereof include rubber polymers; silicone polymers; acrylic polymers. These polymers may be used alone or in combination of two or more.

  As said active energy ray reactive compound, the photoreactive monomer or oligomer which has a functional group which has carbon-carbon multiple bonds, such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, an acetylene group, is mentioned, for example. Specific examples of the photoreactive monomer or oligomer include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc. (Meth) acryloyl group-containing compound; 2 to 5 mer of the (meth) acryloyl group-containing compound; and the like.

  Further, as the active energy ray-reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinyl siloxane; or oligomers composed of the monomers may be used. The resin material (R1) containing these compounds can be cured by high energy rays such as ultraviolet rays and electron beams.

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

  In the resin material (R1) 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 0.00 with respect to 100 parts by weight of the polymer as the base material. 1 to 500 parts by weight, more preferably 1 to 300 parts by weight, and even more preferably 10 to 200 parts by weight.

  The resin material (R1) containing the polymer as the base material and the active energy ray-reactive compound may contain any appropriate additive as necessary. Examples of the additive include an active energy ray polymerization initiator, an active energy ray polymerization accelerator, a crosslinking agent, a plasticizer, and a vulcanizing agent. Any appropriate initiator may be used as the active energy ray polymerization initiator depending on the type of active energy ray used. The active energy ray polymerization initiators may be used alone or in combination of two or more. In the resin material (R1) containing the polymer as the base material and the active energy ray-reactive compound, the content ratio of the active energy ray polymerization initiator is preferably 0.1 with respect to 100 parts by weight of the polymer as the base material. Parts by weight to 10 parts by weight, more preferably 1 part by weight to 5 parts by weight.

  As said active energy ray reactive polymer, the polymer which has a functional group which has carbon-carbon multiple bonds, such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, an acetylene group, is mentioned, for example. Specific examples of the polymer having an active energy ray-reactive functional group include a polymer composed of a polyfunctional (meth) acrylate; a photocationic polymerization type polymer; a cinnamoyl group-containing polymer such as polyvinyl cinnamate; a diazotized amino novolak Resin; polyacrylamide; and the like. Further, as the resin material (R2) containing an active energy ray-reactive polymer, a mixture of an active energy ray-reactive polymer having an allyl group and a compound having a thiol group can also be used. In addition, as long as the resin layer precursor which has practical hardness (viscosity) can be formed before hardening by active energy ray irradiation (for example, when sticking an adhesive sheet), an active energy ray reactive functional group is provided. In addition to the polymer having, an oligomer having an active energy ray-reactive functional group can also be used.

  The resin material (R2) containing the active energy ray-reactive polymer may further contain the active energy ray-reactive compound (monomer or oligomer). Moreover, the resin material (R2) containing the said active energy ray reactive polymer may contain arbitrary appropriate additives as needed. The specific example of an additive is the same as that of the additive which can be contained in the resin material (R1) containing the polymer used as a base material, and an active energy ray reactive compound. In the resin material (R2) containing the active energy ray reactive polymer, the content ratio of the active energy ray polymerization initiator is preferably 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the active energy ray reactive polymer. More preferably, it is 1 to 5 parts by weight.

  The gel fraction of the resin constituting the resin layer is preferably 40% or more, more preferably 50% or more, and more preferably 55% or more. If it is such a range, the fluidity | liquidity of a resin layer will decrease and it can prevent that a cutting groove contacts or reattaches by the time passage after a cutting | disconnection.

  The resin layer may further include beads. Examples of the beads include glass beads and resin beads. If such beads are added to the resin layer, the elastic modulus of the resin layer can be improved, and an adhesive sheet that can process the workpiece with higher accuracy can be obtained. The average particle diameter of the beads is, for example, 0.01 μm to 50 μm. The added amount of the beads is, for example, 10 parts by weight to 200 parts by weight, preferably 20 parts by weight to 100 parts by weight with respect to 100 parts by weight of the entire resin layer.

C. Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer preferably contains a pressure-sensitive adhesive, and more preferably contains a pressure-sensitive adhesive and thermally expandable microspheres.

  The thickness of the pressure-sensitive adhesive layer is preferably 50 μm or less, more preferably 0.1 μm to 50 μm, still more preferably 0.2 μm to 25 μm, and particularly preferably 0.5 μm to 15 μm. When the thickness of the pressure-sensitive adhesive layer is 50 μm or less, it is possible to prevent the cut groove from being narrowed when the cut groove is formed. Can be prevented. In addition, it is possible to prevent problems such as unstable cutting surfaces and generation of cutting waste during cutting. On the other hand, when the thickness of the pressure-sensitive adhesive layer is less than 0.1 μm, there is a possibility that sufficient adhesive force cannot be obtained. In the present specification, the thickness of the pressure-sensitive adhesive layer refers to the surface of the pressure-sensitive adhesive layer opposite to the interface from the interface between the material constituting the resin layer 20 and the pressure-sensitive adhesive 12 constituting the pressure-sensitive adhesive layer 10. The distance to. That is, when the pressure-sensitive adhesive layer includes thermally expandable microspheres, as shown in FIG. 3, the thickness of the pressure-sensitive adhesive layer is evaluated for the portion where the thermally expandable microspheres 11 protrude from the pressure-sensitive adhesive layer 10. Not applicable. The method for discriminating the interface between the material constituting the resin layer 20 and the pressure-sensitive adhesive 12 constituting the pressure-sensitive adhesive layer 10 is as described in the above section B.

  The elastic modulus by the nanoindentation method of the pressure-sensitive adhesive layer at the temperature when the pressure-sensitive adhesive sheet of the present invention is adhered is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and still more preferably 0. .1 MPa to 10 MPa. The elastic modulus of the pressure-sensitive adhesive layer by the nanoindentation method corresponds to the elastic modulus of the adhesive surface by the nanoindentation method. The elastic modulus of the adhesive surface by the nanoindentation method means the elastic modulus measured by the measurement method described in the above section B by selecting a portion where no thermally expandable microspheres exist, that is, the elastic modulus of the adhesive. For example, when an acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive, the temperature at the time of attaching the pressure-sensitive adhesive sheet is 10 ° C. to 80 ° C., and when a styrene-diene block copolymer pressure-sensitive adhesive is used as the pressure-sensitive adhesive, 40 ° C to 120 ° C.

  The gel fraction of the pressure-sensitive adhesive layer is preferably 40% or more, more preferably 50% or more, and more preferably 55% or more. If it is such a range, the fluidity | liquidity of an adhesive layer will decrease and it can prevent that a cutting groove contacts or reattaches by the time passage after a cutting | disconnection.

(Adhesive)
The pressure-sensitive adhesive is preferably one that does not restrain expansion or foaming of the thermally expandable microspheres during heating. Examples of the adhesive include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, and styrene-diene block co-polymers. Polymer-based pressure-sensitive adhesives, radiation-curing types, and creep property-improving pressure-sensitive adhesives in which a hot-melt resin having a melting point of about 200 ° C. or less is blended with these pressure-sensitive adhesives (for example, JP-A-56-61468, JP, 63-17981, A, etc.). Among these, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive is preferable. In addition, you may use the said adhesive individually or in combination of 2 or more types.

  Examples of the acrylic pressure-sensitive adhesive include, 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 monomer components. Etc. Specific examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Undecyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, (me ) Tetradecyl acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate (meta) ) Acrylic acid C1-20 alkyl ester. Especially, the (meth) acrylic-acid alkylester which has a C4-C18 linear or branched alkyl group may be used preferably.

  The acrylic polymer is a unit corresponding to another monomer component copolymerizable with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesion, heat resistance, crosslinkability and the like. May be included. 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, itaconic anhydride Acid anhydride monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, (meth) Hydroxyl group-containing monomers such as hydroxydecyl acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide Sulfonic acid group-containing monomers such as 2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid; (meth) acrylamide, N, N-dimethyl (meta ) (N-substituted) amide monomers such as acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid aminoalkyl monomers such as N, N-dimethylaminoethyl acid, t-butylaminoethyl (meth) acrylate; (meth) methacrylic acid (meth) acrylate, ) Alkoxy acrylate Rutile monomers; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octyl Itaconimide monomers such as itaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylene Succinimide monomers such as succinimide and N- (meth) acryloyl-8-oxyoctamethylenesuccinimide; vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyro Vinyl such as lidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxylic amides, styrene, α-methylstyrene, N-vinylcaprolactam Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, (meth) acrylic acid Glycol acrylic ester monomers such as methoxyethylene glycol and (meth) acrylic acid methoxypolypropylene glycol; (meth) acrylic acid tetrahydrofur Acrylic acid ester monomers having heterocycles such as ril, fluorine (meth) acrylate, silicone (meth) acrylate, halogen atoms, silicon atoms, etc .; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate , (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa Polyfunctional monomers such as (meth) acrylates, epoxy acrylates, polyester acrylates, urethane acrylates; olefinic monomers such as isoprene, butadiene, isobutylene; And vinyl ether monomers such as vinyl ether. These monomer components may be used alone or in combination of two or more.

  Examples of the rubber-based 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 copolymer Examples thereof include rubber-based pressure-sensitive adhesives based on polymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, synthetic rubbers such as modified products thereof, and the like.

  The pressure-sensitive adhesive may contain any appropriate additive as required. Examples of the additive include a crosslinking agent, a tackifier (for example, a rosin tackifier, a terpene tackifier, a hydrocarbon tackifier, etc.), a plasticizer (for example, trimellitic ester plasticizer). , Pyromellitic acid ester plasticizers), pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, UV absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, An antioxidant etc. are mentioned.

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

  Specific examples of the isocyanate-based crosslinking 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 (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), tri Methylolpropane / hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HL”), hexamethylene diisocyanate isocyanate Isocyanurate body (Nippon Polyurethane Industry Co., Ltd. under the trade name "Coronate HX") isocyanate adducts of the like; and the like. The content of the isocyanate-based crosslinking agent can be set to any appropriate amount depending on 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. And more preferably 0.5 to 10 parts by weight.

  Examples of the epoxy crosslinking agent include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane (Mitsubishi Gas). Chemical name, “Tetrad C”), 1,6-hexanediol diglycidyl ether (trade name “Epolite 1600”), neopentyl glycol diglycidyl ether (trade name “Kyoeisha Chemical Co., Ltd. Epolite 1500NP "), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., trade name" Epolite 40E "), propylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., trade name" Epolite 70P "), polyethylene glycol diglycidyl ether (Japan) Product name “Epiol” -400 "), polypropylene glycol diglycidyl ether (Nippon Yushi Co., Ltd., trade name" Epiol P-200 "), sorbitol polyglycidyl ether (Nagase ChemteX Corporation, trade name" Denacol EX-611 "), glycerol polyglycidyl Ether (manufactured by Nagase ChemteX Corporation, trade name “Denacol EX-314”), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “Denacol EX-512”), sorbitan polyglycidyl ether , Trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resor Emissions diglycidyl ether, bisphenol -S- diglycidyl ether, epoxy resins having two or more epoxy groups in the molecule. The content of the epoxy-based crosslinking agent can be set to any appropriate amount depending on the desired adhesive strength, and is typically 0.01 to 10 parts by weight with respect to 100 parts by weight of the base polymer. More preferably, it is 0.03 to 5 parts by weight.

(Thermally expandable microsphere)
As the thermally expandable microsphere, any appropriate thermally expandable microsphere can be used as long as it is a microsphere that can expand or foam by heating. As the thermally expandable microsphere, for example, a microsphere in which a substance that easily expands by heating is encapsulated in an elastic shell can be used. Such thermally expandable microspheres can be produced by any appropriate method, for example, a coacervation method, an interfacial polymerization method, or the like.

  Examples of the material that easily expands when heated include propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, normal hexane, isohexane, heptane, octane, petroleum ether, methane halide, tetraalkylsilane. And low-boiling-point liquids such as azodicarbonamide that is gasified by thermal decomposition.

  Examples of the substance constituting the shell include nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, Carboxylic acid monomers such as citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (Meth) acrylic acid esters such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, β-carboxyethyl acrylate; styrene monomers such as styrene, α-methylstyrene, chlorostyrene ; It includes polymer composed like; acrylamides, substituted acrylamides, methacrylamide, amide monomers such as substituted methacrylamide. The polymer composed of these monomers may be a homopolymer or a copolymer. Examples of the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, acrylonitrile-methacrylonitrile-itaconic acid copolymer. A polymer etc. are mentioned.

  An inorganic foaming agent or an organic foaming agent may be used as the thermally expandable microsphere. Examples of the inorganic foaming agent include ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, various azides and the like. Examples of the organic foaming agent include chlorofluorinated alkane compounds such as trichloromonofluoromethane and dichloromonofluoromethane; azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate. Hydrazine compounds such as p-toluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonyl hydrazide, 4,4′-oxybis (benzenesulfonyl hydrazide), allyl bis (sulfonyl hydrazide); p-toluylene sulfonyl semicarbazide, 4, Semicarbazide compounds such as 4′-oxybis (benzenesulfonyl semicarbazide); Triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; N, N′-dinitrosopentamethylenetetramine, N, '- dimethyl -N, N'-dinitrosoterephthalamide; etc. N- nitroso compounds, and the like.

  A commercially available product may be used as the thermally expandable microsphere. Specific examples of commercially available thermally expandable microspheres are trade names “Matsumoto Microsphere” (grade: F-30, F-30D, F-36D, F-36LV, F-50, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.). F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), trade names “Nippon Philite” "Expansel" (grade: 053-40, 031-40, 920-40, 909-80, 930-120), "Die Form" (grade: H750, H850, H1100, S2320D, S2640D, manufactured by Kureha Chemical Industry Co., Ltd.) M330, M430, M520), “ADVANCEL” manufactured by Sekisui Chemical Co., Ltd. (grade: EML101, EMH204, EHM3) 1, EHM302, EHM303, EM304, EHM401, EM403, EM501) and the like.

  The particle diameter of the thermally expandable microsphere before heating is preferably 0.5 μm to 80 μm, more preferably 5 μm to 45 μm, still more preferably 10 μm to 20 μm, and particularly preferably 10 μm to 15 μm. . Therefore, the particle size before heating of the thermally expandable microspheres is preferably 6 μm to 45 μm, more preferably 15 μm to 35 μm, in terms of the average particle size. The above particle diameter and average particle diameter are values obtained by the particle size distribution measurement method in the laser scattering method.

  The thermally expandable microsphere preferably has an appropriate strength that does not rupture until the volume expansion coefficient is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more. When such a heat-expandable microsphere is used, the adhesive force can be efficiently reduced by heat treatment.

  The content ratio of the heat-expandable microspheres in the pressure-sensitive adhesive layer can be appropriately set according to the desired decrease in adhesive strength. The content ratio of the heat-expandable microsphere is, for example, 1 part by weight to 150 parts by weight, preferably 10 parts by weight to 130 parts by weight, and more preferably 25 parts by weight with respect to 100 parts by weight of the base polymer forming the pressure-sensitive adhesive layer. ~ 100 parts by weight.

D. Base material Examples of the base material include resin sheets, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foamed sheets, and laminates thereof (particularly, laminates including resin sheets). Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene- Vinyl acetate copolymer (EVA), polyamide (nylon), wholly aromatic polyamide (aramid), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluororesin, polyether ether ketone (PEEK) ) And the like. Examples of the nonwoven fabric include nonwoven fabrics made of natural fibers having heat resistance such as nonwoven fabrics including manila hemp; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics and ester resin nonwoven fabrics.

  The thickness of the base material can be set to any appropriate thickness depending on the desired strength or flexibility and the purpose of use. The thickness of the substrate is preferably 1000 μm or less, more preferably 1 μm to 1000 μm, still more preferably 1 μm to 500 μm, particularly preferably 3 μm to 300 μm, and most preferably 5 μm to 250 μm.

  The base material may be subjected to a surface treatment. Examples of the surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, and coating treatment with a primer. By performing such a surface treatment, the adhesion between the resin layer and the substrate can be enhanced. In particular, a coating treatment with an organic coating material is preferable because it improves adhesion and the resin layer is less likely to be thrown and destroyed during heat peeling.

  Examples of the organic coating material include materials described in Plastic Hard Coat Material II (CMC Publishing Co., (2004)). Preferably, a urethane-based polymer, more preferably polyacryl urethane, polyester urethane, or a precursor thereof is used. This is because coating and application to the base material are simple, and various industrial products can be selected and obtained at low cost. The urethane polymer is, for example, a polymer composed of a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound). The organic coating material may contain a chain extender such as polyamine, an anti-aging agent, an oxidation stabilizer and the like as optional additives. Although the thickness of an organic coating layer is not specifically limited, For example, about 0.1 micrometer-10 micrometers are suitable, About 0.1 micrometer-5 micrometers are preferable, About 0.5 micrometer-5 micrometers are more preferable.

E. Production method of pressure-sensitive adhesive sheet As a method for producing the pressure-sensitive adhesive sheet of the present invention, for example, (1) on the release film (release paper), after applying the pressure-sensitive adhesive to form a pressure-sensitive adhesive coating layer, A method of forming a pressure-sensitive adhesive layer by embedding the thermally expandable microspheres in the pressure-sensitive adhesive coating layer with a press or the like, and forming (laminating) a resin layer on the pressure-sensitive adhesive layer; (2) on a release film A pressure-sensitive adhesive layer-forming composition comprising the above-mentioned pressure-sensitive adhesive (and optionally further containing thermally expandable microspheres) to form a pressure-sensitive adhesive coating layer, and a resin layer on the pressure-sensitive adhesive coating layer The method of forming (lamination) is mentioned. When the pressure-sensitive adhesive layer contains thermally expandable microspheres, (3) after forming the pressure-sensitive adhesive coating layer by applying the pressure-sensitive adhesive on the release film, a resin layer is formed on the pressure-sensitive adhesive coating layer. Forming (laminating), then peeling off the release film, and adopting a method of embedding the thermally expandable microspheres by pressing or the like from the surface (adhesive surface) side opposite to the resin layer of the adhesive coating layer Also good. In the methods (1) to (3), the pressure-sensitive adhesive layer can be formed by drying the pressure-sensitive adhesive coating layer, but the drying can be performed at any appropriate timing. The drying may be performed before or after embedding the thermally expandable microspheres. Further, it may be before or after the resin layer is formed. When drying after embedding the heat-expandable microspheres, it is preferable to dry at a temperature at which the heat-expandable microspheres hardly expand or foam. After the operations shown in (1) and (2) above, the release film may be peeled off, and the adhesive surface is protected leaving the release film until the adhesive sheet is put to practical use. Also good.

  When the pressure-sensitive adhesive sheet of the present invention includes a substrate, the pressure-sensitive adhesive sheet is formed on the surface of the resin layer on the side opposite to the pressure-sensitive adhesive layer after the operations (1) to (3) described above. Or it can obtain by sticking a base material through an adhesive. Moreover, the laminated body of a base material and a resin layer and the laminated body of a release film and an adhesive layer (or adhesive coating layer) are produced separately, and these laminated bodies may be bonded together.

  As the method for forming the resin layer, (i) the polymer material or resin material described in the above section B is thermally melted to obtain a molded body in a film form by extrusion molding, and the molded body is converted into the pressure-sensitive adhesive layer (or Pressure-sensitive adhesive coating layer) or a method of laminating on a base material, (ii) a method of applying a resin solution containing the polymer material or resin material to the pressure-sensitive adhesive layer (or pressure-sensitive adhesive coating layer) or the base material, and then drying. (Iii) The resin layer forming composition containing the monomer, oligomer or macromer capable of forming the polymer material or resin material is applied to the pressure-sensitive adhesive layer (or pressure-sensitive adhesive coating layer) or the substrate to form a resin layer. And a method of polymerizing the composition (for example, polymerization by heating, active energy ray irradiation, etc.). According to the method (iii), the amount of solvent and / or heat energy used can be reduced. In the method (ii), the resin solution is applied onto another release film and then dried to obtain a film-like molded product, and then the molded product is applied to the pressure-sensitive adhesive layer (or the pressure-sensitive adhesive coating). Layer) or a substrate. In the method (iii), the resin layer forming composition is applied onto another release film, and then dried to form a resin layer precursor, which is then applied to the adhesive layer (or adhesive layer). Agent coating layer) or a substrate, and then polymerized.

  For example, in the method (iii) above, when forming a resin layer composed of an epoxy polymer, epoxy such as 2,2- (4-hydroxyphenyl) propanediglycidyl ether, bis (4-hydroxyphenyl) methane, etc. A method of heating (for example, 60 ° C. to 120 ° C.) after applying the resin layer forming composition containing the compound and any appropriate curing agent may be employed.

  For example, in the method (iii), when forming a resin layer composed of a urethane polymer, a resin containing an isocyanate compound such as lylene diisocyanate and hexamethylene diisocyanate and a polyol compound such as polyether polyol and polyester polyol. A method of heating (for example, 60 ° C. to 120 ° C.) after applying the layer forming composition may be employed.

  For example, in the method (iii) above, when a resin layer composed of a vinyl polymer is formed, a resin layer forming composition containing a vinyl compound such as vinyl chloride or styrene and any appropriate initiator is used. Can be.

  The composition for forming a resin layer may contain additives such as an initiator, a catalyst, an ultraviolet absorber, and an antioxidant as necessary. Moreover, the said bead may be included.

  When the said resin layer is comprised from the resin material which can be hardened | cured by irradiation of an active energy ray, irradiation of an active energy ray is performed at arbitrary appropriate timings, and an adhesive sheet can be obtained. The irradiation with the active energy ray is performed, for example, after attaching an adherend (workpiece). The irradiation with the active energy ray may be performed stepwise. For example, it may be semi-cured before adhering the adherend and may be fully cured after adhering. The type and amount of active energy rays can be set to any appropriate type and amount depending on the type of resin material constituting the resin layer.

  According to said manufacturing method, the surface at the side of a release film of an adhesive layer (opposite side to a resin layer) turns into an adhesive surface. Since the pressure-sensitive adhesive surface is formed in contact with the release film, even when the pressure-sensitive adhesive layer contains thermally expandable microspheres, the thermally expandable microspheres do not protrude and are flat. On the other hand, thermally expandable microspheres can protrude on the surface of the pressure-sensitive adhesive layer opposite to the pressure-sensitive adhesive surface. In the present invention, since the protruding heat-expandable microspheres are covered with the resin layer, both sides of the pressure-sensitive adhesive sheet are flattened, and therefore the thickness of the pressure-sensitive adhesive layer can be reduced. Such a pressure-sensitive adhesive sheet of the present invention can contribute to excellent cutting accuracy and reduction of cutting waste as a temporary fixing sheet when cutting an electronic component or the like.

F. How to use adhesive sheet (manufacturing method of electronic parts)
According to another aspect of the present invention, a method for manufacturing an electronic component is provided. The manufacturing method of the electronic component of this invention includes sticking the electronic component material (board | substrate) obtained by the large area on the said adhesive sheet, and cut | disconnecting this electronic component material.

  Examples of the electronic parts include parts for semiconductor devices such as silicon wafers; multilayer capacitors: transparent electrodes; and the like.

  In the manufacturing method, first, the pressure-sensitive adhesive sheet is placed on a processing table, and an electronic component material obtained in a large area is attached onto the pressure-sensitive adhesive sheet.

  Thereafter, the electronic component material can be cut by any appropriate method to obtain an electronic component. Examples of the cutting method include a method using a blade such as a rotary blade and a flat blade, a method using a laser beam, and the like. When the electronic component material is cut by pressing with a flat blade, the generation of cutting waste is suppressed and the yield is improved. In the present invention, since the pressure-sensitive adhesive layer can be thinned, even if the electronic component material is cut by pressing with a flat blade, the cut piece contacts or reattaches, the cut surface becomes slanted, or S It is possible to prevent the character from becoming unstable when it becomes a character, or chipping from occurring during cutting. Further, in the present invention, even when a thin blade is used for cutting, the above-described effects can be obtained, and manufacturing loss caused by the thickness of the blade (loss due to a gap generated between chips after cutting) can be reduced. it can. In the manufacture of a more miniaturized electronic component, since the number of cut surfaces is large, the present invention that can reduce the manufacturing loss as described above is particularly useful. In the cutting process, the cutting blade may or may not reach the resin layer of the pressure-sensitive adhesive sheet of the present invention. Preferably, the cutting blade reaches the resin layer. If it does in this way, the reattachment (contact) prevention effect of a cut piece will become remarkable.

  In the cutting process, cutting may be performed under heating. For example, the processing table may be heated to 30 ° C. to 150 ° C. for cutting.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. The evaluation methods in the examples are as follows. In Examples, unless otherwise specified, “parts” and “%” are based on weight.

(1) Measurement of pressure-sensitive adhesive layer and resin layer thickness in Raman mapping The pressure-sensitive adhesive sheets obtained in Examples 1 to 3, 5, 6 and 12 to 15 were sectioned with a microtome to prepare measurement samples. The cross section of the measurement sample was subjected to spectroscopic analysis by Raman spectrum using alpha300RSA manufactured by WITec, and the peak derived from the component added only to the resin layer (for example, the active energy ray-reactive oligomer (UV1700B) in Example 3). Based on the peak intensity at 1640 cm ⁻¹ , the thicknesses of the resin layer and the pressure-sensitive adhesive layer were measured. Using Example 3 as a representative example, Raman mapping in the measurement is shown in FIG. The surface where the abundance of components added only to the resin layer is clearly different is defined as the interface 1, and the distance from the interface 1 to the surface of the adhesive layer opposite to the interface 1 is the thickness of the adhesive layer, from the interface 1 The distance to the surface of the resin layer opposite to the interface was taken as the thickness of the resin layer.
The measurement conditions for Raman mapping measurement are as follows.
Excitation wavelength: 532 nm
Measurement wave number range: 300 to 3600 cm ⁻¹
・ Grating: 600 gr / mm
Objective lens: x100
・ Measurement time: 0.2 sec / 1 spectrum ・ Measurement range: 20 × 40 μm
-Number of measurements: 100 x 200 points-Detector: EMCCD

(2) Measurement of pressure-sensitive adhesive layer and resin layer thickness with SEM The pressure-sensitive adhesive sheets obtained in Examples 4, 7 to 11, 16, 17 and Comparative Example 1 were cut with a trimming cutter in the thickness direction, and Pt-Pd After performing the sputtering treatment, the cut surface is observed using an S3400N low-vacuum scanning electron microscope (SEM) manufactured by Hitachi High-Technologies Corporation to determine the interface 1, and the interface 1 is the opposite side of the adhesive layer from the interface 1 The distance to the surface was the thickness of the pressure-sensitive adhesive layer, and the distance from the interface 1 to the surface of the resin layer opposite to the interface was the thickness of the resin layer. FIG. 6 shows a SEM image of the cross section of the pressure-sensitive adhesive sheet, with Example 11 as a representative example.
The measurement conditions for SEM observation are as follows.
-Observation image: ESED image-Acceleration voltage: 10 kV
・ Magnification: 600 times

(3) Measurement of elastic modulus The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut in the thickness direction with a microtome, and the elastic modulus of the cut surface was measured with a nanoindenter.
More specifically, with respect to the resin layer, the surface of the resin layer (surface opposite to the adhesive surface) that is substantially perpendicular to the cut surface and the cut surface that is about 3 μm away from the surface were measured. An elastic modulus was obtained by numerically processing a displacement-load hysteresis curve obtained by pressing a probe (indenter) against an object to be measured using software (triboscan) attached to the measuring device. In Table 1, the elastic modulus measured on the surface of the cut surface separated by about 3 μm from the surface is shown (average value of three measurements).
The nanoindenter apparatus and measurement conditions are as follows.
Apparatus and measurement conditions / apparatus: Nanoindenter; Tribodenter manufactured by Hystron Inc.
・ Measurement method: Single indentation method ・ Measurement temperature: 25 ° C
・ Push-in speed: about 1000nm / sec
・ Indentation depth: about 800nm
・ Tip: Diamond, Berkovich type (triangular pyramid type)

(4) Adhesive strength measurement (adhesive strength before heating (before expanding thermally expandable microspheres))
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut into a size of width: 20 mm and length: 140 mm, and a polyethylene terephthalate film (trade name “Lumirror S-10” Toray Industries, Inc. as an adherend was formed on the pressure-sensitive adhesive surface. Manufactured in a thickness of 25 μm and a width of 30 mm) in a state of protruding by 5 mm on the left and right sides in accordance with JIS Z 0237: 2009, a 2 kg roller was reciprocated once to prepare a measurement sample. The measurement sample was set in a tensile tester with a thermostatic bath (trade name “Shimadzu Autograph AG-120kN”, manufactured by Shimadzu Corporation) and left for 30 minutes. Thereafter, the load was measured when the adherend was peeled from the pressure-sensitive adhesive sheet in the length direction under the conditions of peeling angle: 180 °, peeling speed (tensile speed): 300 mm / min, and the maximum load ( The maximum value of the load excluding the peak top at the initial stage of measurement was determined, and the maximum load divided by the tape width was defined as the adhesive strength (N / 20 mm width). The above operation was performed in an atmosphere of temperature: 23 ± 3 ° C. and humidity: 65 ± 5% RH.
(Adhesive strength after heating (after expanding or foaming thermally expandable microspheres))
A measurement sample was prepared in the same manner as described above, and the measurement sample was put into a hot air dryer. After leaving still for 1 minute under the maximum expansion temperature (after-mentioned) of a thermally expansible microsphere in a hot air dryer, the to-be-adhered body was peeled similarly to the above, and the adhesive force was measured. The operation before and after the charging into the hot air dryer was performed in an atmosphere of temperature: 23 ± 3 ° C. and humidity: 65 ± 5% RH.

(5) Surface roughness measurement About the adhesive sheet obtained by the Example and the comparative example, after expanding or foaming a thermally expansible microsphere, surface roughness Ra of the adhesive surface was measured. The expansion or foaming of the heat-expandable microspheres was performed by standing in a hot air dryer for 1 minute at the maximum expansion temperature (described later) of the heat-expandable microspheres. The surface roughness was measured using a laser microscope “OLS4000” manufactured by Olympus.

(6) Evaluation of small piece separability after cutting A laminated ceramic sheet of 40 mm × 50 mm (thickness 500 μm) was bonded to the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples. The multilayer ceramic sheet on the pressure-sensitive adhesive sheet was cut into a 1 mm × 0.5 mm piece shape with a cutting device “G-CUT8AA” manufactured by UHT. The laminated ceramic sheet on the pressure-sensitive adhesive sheet was placed along the side of a cylinder having a diameter of 30 mm. A heat treatment is performed at a predetermined temperature (maximum expansion temperature of the thermally expandable microsphere (described later)) in a state where it is installed on the cylinder, and the thermally expandable microsphere is expanded to peel off the small pieces from the adhesive sheet. The number of chips with no separation between the chips was counted. The number obtained by dividing the number of non-separated chips by 100% when completely separated was used as an index of separability. The index is less than 2%, the index is 2% or more and less than 5%, the index is 5% or more and less than 15%, and the index is 15% or more.
Details of the composition of the multilayer ceramic sheet and the cutting conditions of the cutting apparatus are as follows.
(Laminated ceramic sheet)
By adding 100 parts of barium titanate powder, 15 parts of polyvinyl butyral resin, 6 parts of bis (2-ethylhexyl) phthalate, and 2 parts of diglycerin stearate to a toluene solvent, and mixing and dispersing with a ball mill disperser. A dielectric toluene solution was obtained. Apply this solution to the silicone release agent-treated surface of a polyethylene terephthalate film with a silicone release agent-treated surface (manufactured by Mitsubishi Polyester Film Co., Ltd., trade name “MRF38”, thickness: 38 μm) so that the thickness after evaporation of the solvent is 50 μm. It was applied and dried to obtain a ceramic sheet. A plurality of the obtained ceramic sheets were laminated so as to have a thickness of 500 μm to obtain a laminated ceramic sheet.
(Cutting conditions)
Cutting temperature: 60 ° C., cutting depth (remaining amount from the table surface): about 20 μm
Cutting blade: “U-BLADE2” manufactured by UHT, blade thickness: 50 μm, blade edge angle: 15 °

(7) Cut surface cut property evaluation In the same manner as in the above (6), the multilayer ceramic sheet was cut into a square shape so as to be a small piece of 1 mm x 0.5 mm. Select any 10 pieces from among the cut pieces, observe the cut surface with a magnifying glass at 50 magnification, check for chipping (lamination of the laminated ceramic sheet generated by the cutting process), and check the chipping generated in 10 pieces. The average of the total number was used as an index. When the index is 0 to less than 10 places, ◎, 10 or more and less than 20 places, ◯, 20 or more and less than 40 places, and 40 or more places as x.

(8) Evaluation of cutting groove disappearance level The adhesive sheets obtained in the examples and comparative examples were cut through the adhesive layer from the pressure-sensitive adhesive layer side using a cutting device “G-CUT8AA” manufactured by UHT. About the virtual surface A corresponding to the cross-sectional shape in the line width direction of the cutting groove in the pressure-sensitive adhesive layer, the area S1 of the virtual surface A immediately after the cutting groove was formed and one hour passed at 25 ° C. after the cutting groove was formed. The ratio (S2 / S1) with the area S2 of the subsequent virtual surface A was obtained. The area of the virtual surface A was measured by cutting the adhesive sheet with a trimming cutter in the thickness direction, and observing the cut surface using an S3400N low vacuum scanning electron microscope (SEM) manufactured by Hitachi High-Technologies Corporation.
(Cutting groove forming conditions)
Cutting temperature: 60 ° C., cutting depth (remaining amount from the table surface): about 15 μm
Cutting blade: “U-BLADE2” manufactured by UHT, blade thickness: 50 μm, blade edge angle: 15 °

The polymer preparation method is described below. In addition, unless it refuses with a part here, let it be a weight part.
[Production Example 1] Preparation of polymer 1 In toluene, 100 parts of butyl acrylate, 5 parts of acrylic acid, and 0.2 part of benzoyl peroxide as a polymerization initiator were added and then heated to prepare an acrylic copolymer. A toluene solution of the combined polymer 1 was obtained.

[Production Example 2] Preparation of polymer 2 In toluene, 30 parts of 2-ethylhexyl acrylate, 70 parts of ethyl acrylate, 4 parts of 2-hydroxyethyl acrylate, 5 parts of N-phenylmaleimide, and peroxide as a polymerization initiator After adding 0.2 part of benzoyl, the mixture was heated to obtain a toluene solution of an acrylic copolymer (polymer 2).

[Production Example 3] Preparation of polymer 3 In toluene, 30 parts of 2-ethylhexyl acrylate, 70 parts of ethyl acrylate, 4 parts of 2-hydroxyethyl acrylate, 5 parts of methyl methacrylate, and benzoyl peroxide 0 as a polymerization initiator After adding 2 parts, the mixture was heated to obtain a toluene solution of an acrylic copolymer (polymer 3).

[Production Example 4] Preparation of polymer 4 In toluene, 50 parts of butyl acrylate, 50 parts of ethyl acrylate, 5 parts of acrylic acid, 0.1 part of 2-hydroxyethyl acrylate, and benzoyl peroxide 0 as a polymerization initiator After adding 2 parts, the mixture was heated to obtain a toluene solution of an acrylic copolymer (polymer 4).

[Production Example 5] Preparation of polymer 5 After adding 70 parts of methyl acrylate, 30 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, and 0.2 part of benzoyl peroxide as a polymerization initiator in ethyl acetate To obtain an ethyl acetate solution of an acrylic copolymer (Polymer 5).

[Production Example 6] Preparation of polymer 6 In toluene, 50 mol of butyl acrylate, 50 mol of ethyl acrylate, 22 mol of 2-hydroxyethyl acrylate, and benzoyl peroxide (butyl acrylate, ethyl acrylate, and 2- After adding 0.2 part) to a total of 100 parts of hydroxyethyl acrylate, the mixture was heated to obtain a copolymer solution. To this copolymer solution, 2-isocyanatoethyl acrylate in an amount corresponding to 80 mol% of the hydroxyl groups derived from 2-hydroxyethyl acrylate in the solution was added and then heated to derive from the 2-hydroxyethyl acrylate. By adding 2-isocyanatoethyl methacrylate to the hydroxyl group, a toluene solution of an acrylic copolymer (polymer 6) having a methacrylate group in the side chain was obtained.

[Production Example 7] Preparation of polymer 7 In toluene, 80 moles of butyl acrylate, 30 moles of acryloyl morpholine, 20 moles of 2-hydroxyethyl acrylate, and benzoyl peroxide (butyl acrylate, acryloyl morpholine and 2- After adding 0.2 part) to a total of 100 parts of hydroxyethyl acrylate, the mixture was heated to obtain a copolymer solution. To this copolymer solution, 2-isocyanatoethyl acrylate in an amount corresponding to 50 mol% of the hydroxyl groups derived from 2-hydroxyethyl acrylate in the solution was added and then heated to derive from the 2-hydroxyethyl acrylate. By adding 2-isocyanatoethyl methacrylate to the hydroxyl group, a toluene solution of an acrylic copolymer (polymer 7) having a methacrylate group in the side chain was obtained.

[Example 1]
(Formation of adhesive layer precursor layer)
Toluene solution of polymer 2 prepared in Production Example 2 (polymer 2: 100 parts), 1 part of an isocyanate-based crosslinking agent (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.), and a terpene phenol resin ( Sumitomo Bakelite Co., Ltd., trade name “Sumilite Resin PR12603” 5 parts, thermally expandable microspheres (Matsumoto Yushi Seiyaku Co., Ltd., trade name “Matsumoto Microsphere F-50D”, foaming (expansion) start temperature: 95 A mixture was prepared by mixing 40 parts of (C ° -105 ° C., maximum expansion temperature: 125 ° C.-135 ° C., average particle size 10 μm-18 μm). The same solvent (toluene) as the solvent in the mixed solution was further added to the mixed solution to adjust the viscosity to a viscosity that was easy to apply. This mixed solution is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (trade name “MRF38”, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., thickness: 38 μm) so that the thickness after solvent evaporation (drying) is 10 μm. And then dried to form an adhesive layer precursor layer on the polyethylene terephthalate film.
(Formation of resin layer precursor layer)
A toluene solution of polymer 1 prepared in Production Example 1 (polymer 1: 100 parts) and a mixture of dipentaerythritol pentaacrylate and hexaacrylate as an active energy ray-reactive oligomer (trade name “Aronix M404” manufactured by Toagosei Co., Ltd.) ) 20 parts, 2 parts of an isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane, trade name “Coronate L”) and 3 parts by weight of an energy ray polymerization initiator (trade name “Irgacure 651”, manufactured by BASF Japan) To prepare a mixed solution. The same solvent (toluene) as the solvent in the mixed solution was further added to the mixed solution to adjust the viscosity to a viscosity that was easy to apply. Apply to a polyethylene terephthalate film with a silicone release agent-treated surface (Mitsubishi Chemical Polyester Film Co., Ltd., trade name “MRF38”, thickness: 38 μm) using an applicator so that the thickness after solvent evaporation (drying) is 20 μm. Then, it was dried to form a resin layer precursor layer on the polyethylene terephthalate film.
(Formation of adhesive sheet 1)
The said adhesive layer precursor layer and the resin layer precursor layer were bonded together. Subsequently, ultraviolet irradiation with an integrated light quantity of 300 mJ / cm 2 was performed from the resin layer precursor layer side using an ultraviolet irradiation machine “UM810 (high pressure mercury lamp light source)” (manufactured by Nitto Seiki Co., Ltd.). Then, the polyethylene terephthalate film with a silicone release agent-treated surface was peeled off to obtain a pressure-sensitive adhesive sheet 1 (pressure-sensitive adhesive layer thickness: 10 μm, resin layer thickness: 25 μm).

[Examples 2 to 15, Comparative Example 1]
The type and amount of the polymer, crosslinking agent, tackifier and thermally expandable microsphere when forming the pressure-sensitive adhesive layer precursor layer are set as shown in Table 1, and the polymer when forming the resin layer precursor layer, A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the types and blending amounts of the active energy ray-reactive oligomer, the crosslinking agent and the energy ray polymerization initiator were set as shown in Table 1.
In Examples 2 to 5, 8, 10, 13 to 15 and Comparative Example 1, when forming the resin layer precursor layer, instead of the polyethylene terephthalate film with a silicone release agent-treated surface, a PET film (thickness: 100 [mu] m) was applied to the mixed solution, and an adhesive sheet having a PET film (base material) was obtained without peeling off the PET film. Moreover, in Example 4 and Comparative Example 1, the adhesive sheet was obtained without performing ultraviolet irradiation.
The details of the crosslinking agent, tackifier, thermally expandable microsphere, active energy ray reactive oligomer, and energy ray polymerization initiator described in Table 1 are as follows.
<Crosslinking agent>
Tetrad C: Mitsubishi Gas Chemical Company, trade name “Tetrad C”, epoxy cross-linking agent <tackifier>
PR51732: Product name “Sumilite Resin PR51732” manufactured by Sumitomo Bakelite Co., Ltd.
S145: Product name “YS Polystar S145” manufactured by Yasuhara Chemical Co., Ltd.
U130: Product name “YS Polystar U130” manufactured by Yasuhara Chemical Co., Ltd.
T160: Yasuhara Chemical Co., Ltd., trade name “YS Polystar T160”
<Thermal expandable microsphere>
F-30D: manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name “Matsumoto Microsphere F-30D”, foaming (expansion) start temperature: 70 ° C. to 80 ° C., maximum expansion temperature: 110 ° C. to 120 ° C., average particle size 10 μm to 18 μm
F-65D: Matsumoto Yushi Seiyaku Co., Ltd., trade name “Matsumoto Microsphere F-65D”, foaming (expansion) start temperature: 105 ° C. to 115 ° C., maximum expansion temperature: 145 ° C. to 155 ° C., average particle size 12 μm 18 μm
FN-180SSD: Matsumoto Yushi Seiyaku Co., Ltd., trade name “Matsumoto Microsphere FN-180SSD”, foaming (expansion) start temperature: 135 ° C. to 150 ° C., maximum expansion temperature: 165 ° C. to 180 ° C., average particle size 15 μm to 25 μm
F-260D: Made by Matsumoto Yushi Seiyaku Co., Ltd., trade name “Matsumoto Microsphere F-260D”, foaming (expansion) start temperature: 190 ° C. to 200 ° C., maximum expansion temperature: 250 ° C. to 260 ° C., average particle size 20 μm to 35 μm
<Active energy ray reactive oligomer>
UV1700B: manufactured by Nippon Synthetic Chemical Co., Ltd., trade name “purple UV-1700B”, ultraviolet curable urethane acrylate UV7620EA: manufactured by Nippon Synthetic Chemical Co., Ltd., trade name “purple UV-7620EA”, ultraviolet curable urethane acrylate UV3000B: Nippon Synthetic Chemical Co., Ltd. Product name “purple light UV-3000B”, UV curable urethane acrylate M321: manufactured by Toa Gosei Co., Ltd., product name “Aronix M321”, trimethylolpropane PO-modified triacrylate (average added moles of propylene oxide (PO): 2) Mole)
UV7630B: manufactured by Nippon Synthetic Chemical Co., Ltd., trade name “purple light UV-7630B”, ultraviolet curable urethane acrylate <energy ray polymerization initiator>
I184: BASF Corporation, trade name “Irgacure 184”
I2959: BASF, trade name “Irgacure 2959”
I6511: BASF, trade name “Irgacure 651”

[Example 16]
Toluene solution of polymer 1 prepared in Production Example 1 (polymer 1: 100 parts), epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name “Tetrad C”) 0.8 parts, and terpene as a tackifier 30 parts of phenolic resin (trade name “YS Polystar S145”, manufactured by Yashara Chemical Co., Ltd.) and thermally expandable microspheres (trade name “Matsumoto Microsphere F-50D”, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), foaming (expansion) start temperature : 95 ° C. to 105 ° C., maximum expansion temperature: 125 ° C. to 135 ° C., average particle diameter of 10 μm to 18 μm) was mixed with 30 parts to prepare a mixed solution. The same solvent (toluene) as the solvent in the mixed solution was further added to the mixed solution to adjust the viscosity to a viscosity that was easy to apply. This mixed solution is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (trade name “MRF38”, thickness: 38 μm, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the thickness after solvent evaporation (drying) is 30 μm. And then dried to form an adhesive layer precursor layer on the polyethylene terephthalate film.
The pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer precursor layer was bonded to a mat-treated surface of a polyethylene terephthalate film (trade name “Lumirror type X42”, manufactured by Toray Industries, Inc., thickness: 50 μm) as a resin layer with a hand roller. By carrying out autoclave treatment (40 ° C., 5 kgf / cm 2, 10 minutes), an adhesive sheet (adhesive layer (thickness: 30 μm) / resin layer (polyethylene terephthalate, thickness: 50 μm)) was obtained.

[Example 17]
Toluene solution of polymer 4 prepared in Production Example 4 (polymer 4: 100 parts), epoxy cross-linking agent (trade name “Tetrad C” manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.8 parts, and terpene as a tackifier 5 parts of phenolic resin (trade name “YS Polystar S145” manufactured by Yashara Chemical Co., Ltd.) and thermally expandable microspheres (trade name “Matsumoto Microsphere F-50D” manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), foaming (expansion) start temperature : 95 ° C. to 105 ° C., maximum expansion temperature: 125 ° C. to 135 ° C., average particle diameter of 10 μm to 18 μm) was mixed with 30 parts to prepare a mixed solution. The same solvent (toluene) as the solvent in the mixed solution was further added to the mixed solution to adjust the viscosity to a viscosity that was easy to apply. This mixed solution is applied to a polyethylene terephthalate film with a silicone release agent-treated surface (trade name “MRF38”, thickness: 38 μm, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the thickness after solvent evaporation (drying) is 40 μm. And then dried to form an adhesive layer precursor layer on the polyethylene terephthalate film.
A mixed solvent of ethyl acetate and dimethylformamide (ethyl acetate) with a wire bar (10th) on one side of a polyethylene terephthalate film (Mitsubishi Resin Diafix (PG-CHI (FG, thickness 200 μm)) as a resin layer. : Dimethylformamide = 1: 10 (volume%)) and the adhesive surface of the pressure-sensitive adhesive layer precursor layer was bonded to the coated surface with a hand roller, and dried with a hot air dryer at 80 ° C. for 3 minutes. Thus, an adhesive sheet (adhesive layer (thickness: 40 μm) / resin layer (polyethylene terephthalate, thickness: 200 μm)) was obtained.

  The manufacturing method and pressure-sensitive adhesive sheet of the present invention can be suitably used for manufacturing chip-shaped electronic components such as semiconductor chips.

DESCRIPTION OF SYMBOLS 10 Adhesive layer 11 Thermally expansible microsphere 12 Adhesive 20 Resin layer 30 Base material 100, 200, 300 Adhesive sheet

Claims (6)

An adhesive layer, and a resin layer disposed on one side of the adhesive layer,
The pressure-sensitive adhesive layer contains heat-expandable microspheres, and when the heat-expandable microspheres are expanded or foamed by heating, the surface roughness Ra of the surface of the pressure-sensitive adhesive layer opposite to the resin layer Is 3 μm or more,
The elastic modulus of the resin layer by a nanoindentation method at 25 ° C. is 34 MPa to 1000 MPa ,
From the pressure-sensitive adhesive layer side, when the cut groove is formed so as to penetrate the pressure-sensitive adhesive layer, the cut groove does not disappear after 1 hour at 25 ° C. after the formation of the cut groove.
Adhesive sheet.   The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 50 μm or less.   The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the pressure-sensitive adhesive force is reduced by heating.   The pressure-sensitive adhesive according to any one of claims 1 to 3, wherein a ratio (a2 / a1) between the pressure-sensitive adhesive force (a1) before heating and the pressure-sensitive adhesive force (a2) after heating is 0.0001 to 0.5. Sheet.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, further comprising a base material on a side of the resin layer opposite to the pressure-sensitive adhesive layer. After sticking an electronic component material on the pressure-sensitive adhesive sheet according to any one of claims 1 to 5,
Cutting the electronic component material,
Manufacturing method of electronic components.