JP2019009260A - Dicing tape built-in adhesive sheet - Google Patents

Abstract

To provide a dicing tape (DT) built-in adhesive sheet suitable for realizing good pickup of a semiconductor chip with adhesive film from a DT.SOLUTION: A DT built-in adhesive sheet X includes a DT20 having a radiation curable adhesive layer 22 on the surface, and an adhesive sheet. The adhesive sheet has a laser mark (LM) layer 11 and an adhesive layer 12. The adhesive layer side surface of the adhesive sheet shows a peeling adhesive force of 5 N/10 mm or more for a Si wafer, in the peeling test under conditions of 23°C, peeling angle 180° and tensile rate 300 mm/min. First peeling adhesive force between the hardened adhesive layer 22 and the adhesive sheet, in the peeling test under above-mentioned conditions, is 0.15 N/20 mm or less. The difference between second peeling adhesive force in the peeling test under above-mentioned conditions, and the first peeling adhesive force is 0.12 N/20 mm or less, between the hardened adhesive layer 22 after preservation of nine days at 50°C and the adhesive sheet.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a dicing tape-integrated adhesive sheet that can be used in the manufacturing process of a semiconductor device.

  In the manufacturing process of a semiconductor device, a semiconductor wafer as a workpiece and a dicing tape-integrated adhesive sheet of a corresponding size are bonded together, and then the semiconductor wafer is separated into individual pieces and the semiconductor with an adhesive film Tips may be obtained. As such a dicing tape-integrated adhesive sheet, a dicing tape-integrated back surface protective film is known.

  The dicing tape-integrated back surface protective film has, for example, a dicing tape having a laminated structure including a base material and an adhesive layer, and a thermosetting back surface protective film in close contact with the adhesive layer. Such a dicing tape-integrated back surface protective film is used, for example, as follows. First, a semiconductor wafer is bonded onto the back surface protective film of the dicing tape integrated back surface protective film. Next, the semiconductor wafer is separated into semiconductor chips by blade dicing while the semiconductor wafer is held on the dicing tape-integrated back surface protective film (dicing step). In the dicing step, the back surface protective film is also cut together with the semiconductor wafer on the dicing tape so that a plurality of adhesive film pieces each in close contact with the semiconductor chip are generated from the back surface protective film. Next, after a washing process, each semiconductor chip with an adhesive film on the dicing tape is picked up from the dicing tape (pickup process). At this time, the adhesive film in the semiconductor chip with the adhesive film to be picked up needs to be appropriately peeled from the pressure-sensitive adhesive layer of the dicing tape. For example, as described above, the dicing tape-integrated back surface protective film is used in the process of obtaining a semiconductor chip with an adhesive film of a chip-equivalent size for protecting a semiconductor chip back surface. The technology related to such a dicing tape-integrated back surface protective film is described in, for example, Patent Documents 1 and 2 below.

JP 2011-151360 A International Publication No. 2014/092200

  Conventionally, the thermosetting back surface protective film on the dicing tape in the dicing tape-integrated back surface protective film is bonded to a semiconductor wafer and then thermally cured by heating to increase the adhesion to the wafer. However, such heat curing of the back surface protective film also increases the adhesion of the back surface protective film to the dicing tape or its adhesive layer. Such an increase in adhesion force may inhibit peeling of the adhesive film of the semiconductor chip with the adhesive film from the dicing tape pressure-sensitive adhesive layer in the pick-up process as described above, and therefore with the adhesive film. In some cases, the pickup of the semiconductor chip may be hindered.

  Moreover, the thermosetting back surface protective film that is in an uncured state in the dicing tape-integrated back surface protective film adheres to the dicing tape pressure-sensitive adhesive layer as the storage period before use of the dicing tape-integrated back surface protective film becomes longer. Power tends to increase gradually. Such an increase in adhesion force may inhibit peeling of the adhesive film of the semiconductor chip with the adhesive film from the dicing tape pressure-sensitive adhesive layer in the pick-up process as described above, and therefore with the adhesive film. In some cases, the pickup of the semiconductor chip may be hindered.

  The present invention has been conceived under the circumstances as described above, and is a dicing tape-integrated adhesive sheet suitable for realizing a good pickup of a semiconductor chip with an adhesive film from a dicing tape. The purpose is to provide

  According to the present invention, an adhesive sheet integrated with a dicing tape is provided. The dicing tape-integrated adhesive sheet includes a dicing tape and an adhesive sheet. The dicing tape has a laminated structure including a radiation curable pressure-sensitive adhesive layer for forming an adhesive surface and a base material. The adhesive sheet has a laminated structure including a laser mark layer for forming a marking target surface and an adhesive layer for forming a workpiece attaching surface, and an adhesive layer in a dicing tape on the laser mark layer side Moreover, it is in close contact with the adhesive surface in a peelable manner. The surface on the side of the adhesive layer in the adhesive sheet exhibits a peel adhesive strength of 5 N / 10 mm or more in a peel test on a silicon wafer at 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. The peel adhesive strength is preferably 6 N / 10 mm or more, more preferably 7 N / 10 mm or more. The surface on the laser mark layer side of the adhesive sheet exhibits a peel adhesive strength of 0.2 N / 10 mm or less, preferably 0.1 N / 10 mm or less, more preferably, in a peel test under the above conditions with respect to a silicon wafer. Indicates a peel adhesive strength of 0.07 N / 10 mm or less. The first peel adhesive strength in the peel test under the above conditions between the radiation-cured pressure-sensitive adhesive layer and the adhesive sheet is 0.15 N / 20 mm or less, preferably 0.13 N / 20 mm or less, more preferably Is 0.09 N / 20 mm or less. A second peel adhesive strength in a peel test under the above conditions between the radiation-cured pressure-sensitive adhesive layer and the adhesive sheet after storage of the dicing tape-integrated adhesive sheet at 50 ° C. for 9 days; The difference from 1 peel adhesive strength is 0.12 N / 20 mm or less, preferably 0.1 N / 20 mm or less, more preferably 0.07 N / 20 mm or less. The dicing tape-integrated adhesive sheet having such a configuration can be used in the process of manufacturing a semiconductor device. Specifically, the dicing tape-integrated adhesive sheet of the present invention is a chip-corresponding chip for protecting a semiconductor chip back surface as a dicing tape-integrated back surface protective film employing a so-called back surface protective film configuration for the adhesive sheet. It can be used to obtain a semiconductor chip with an adhesive film.

  As described above, the surface on the adhesive layer side of the adhesive sheet of this dicing tape-integrated adhesive sheet is 23 ° C., a peeling angle of 180 °, and a tensile speed of 300 mm / min. In this case, the peel adhesive strength is 5 N / 10 mm or more, preferably 6 N / 10 mm or more, more preferably 7 N / 10 mm or more. The configuration in which the adhesive sheet exhibits such a high peel adhesive strength with respect to the silicon wafer realizes good holding of a work such as a semiconductor wafer by the adhesive sheet integrated with the dicing tape or the adhesive sheet. Suitable. The dicing tape-integrated adhesive sheet having such a configuration does not require curing by heating to increase the adhesion to the workpiece of the adhesive sheet after being bonded to the workpiece. It is suitable for avoiding or suppressing an increase in the adhesion of the adhesive sheet to the tape adhesive layer. Therefore, such a dicing tape-integrated adhesive sheet is suitable for realizing a good pickup of the semiconductor chip with an adhesive film from the dicing tape, for example, in the above-described pickup process.

  As described above, the surface of the adhesive sheet of the dicing tape-integrated adhesive sheet on the laser mark layer side is a peel test under the conditions of 23 ° C., a peel angle of 180 °, and a pulling speed of 300 mm / min. In this case, the peel adhesive strength is 0.2 N / 10 mm or less, preferably 0.1 N / 10 mm or less, more preferably 0.07 N / 10 mm or less. Further, as described above, the peel adhesive force (first peel adhesive force) in the peel test under the above conditions between the radiation-cured pressure-sensitive adhesive layer and the adhesive sheet is 0.15 N / 20 mm or less. , Preferably 0.13 N / 20 mm or less, more preferably 0.09 N / 20 mm or less. These configurations relating to low peel adhesive strength are suitable for ensuring the peelability of the adhesive sheet from the dicing tape pressure-sensitive adhesive layer, and thus, for example, in the pickup process as described above, the semiconductor chip with an adhesive film from the dicing tape Suitable for realizing a good pickup. In addition, these configurations relating to low peel adhesive strength are, for example, when the adhesive strength of the adhesive sheet to the dicing tape pressure-sensitive adhesive layer increases with time during the storage period before use of the dicing tape-integrated adhesive sheet. Even if it exists, it is suitable in order to avoid that the said adhesive force becomes excessive, and the adhesive layer and adhesive sheet which were radiation-cured after storage for 9 days at 50 degreeC of this dicing tape integrated adhesive sheet The difference between the peel adhesive strength (second peel adhesive strength) and the above-mentioned first peel adhesive strength in the peel test under the conditions of 23 ° C., peel angle 180 °, and tensile speed 300 mm / min. 12 N / 20 mm or less, preferably 0.1 N / 20 mm or less, more preferably 0.07 N / 20 mm or less. That is, the said structure regarding low peeling adhesive force is suitable when ensuring storage stability regarding the adhesiveness between a dicing tape adhesive layer and an adhesive sheet or its laser mark layer. Even if the adhesive force of the adhesive sheet to the dicing tape pressure-sensitive adhesive layer increases with time, it can be avoided that the adhesive force becomes excessive from the dicing tape, for example, in the above-described pickup process. This contributes to realizing a good pickup of a semiconductor chip with an adhesive film.

  As described above, the dicing tape-integrated adhesive sheet of the present invention is suitable, for example, as a dicing tape-integrated back surface protective film to realize a good pickup of a semiconductor chip with an adhesive film from a dicing tape.

  In the above-mentioned adhesive sheet, the laser mark layer is preferably a cured thermosetting layer. Such a configuration is suitable for suppressing an increase in the adhesive force with respect to the dicing tape pressure-sensitive adhesive layer over time in the adhesive sheet. In addition, the configuration in which the laser mark layer is a thermosetting layer is used when the laser mark layer side surface of the adhesive sheet undergoes a high-temperature process such as a so-called reflow process after being engraved by laser marking. Suitable for ensuring the visibility of

  In the above-described adhesive sheet, preferably, the adhesive layer is a thermoplastic layer. Such a configuration contributes to the realization of the above-described high peel adhesive force in the adhesive sheet, that is, high adhesion to a workpiece such as a wafer. In the adhesive sheet of the dicing tape integrated adhesive sheet, when the laser mark layer is a thermosetting layer and the adhesive layer is a thermoplastic layer, the adhesive sheet is, for example, a single thermosetting layer. It is more preferable than the case where the adhesive sheet is cut in the expanding process for cleaving described below. That is, in the adhesive sheet, the laser mark layer is a thermosetting layer and the adhesive layer is a thermoplastic layer. Therefore, it is suitable for achieving both ensuring of good cutting ability and realization of good cleaving property.

  In the above-mentioned adhesive sheet, the value of the ratio of the thickness of the laser mark layer to the thickness of the adhesive layer is preferably 0.65 to 12, more preferably 0.75 to 7.5, and more preferably 0.5. 85 to 5.5. Such a configuration is preferable in order to achieve both the characteristics required for the laser mark layer side surface in the adhesive sheet and the characteristics required for the adhesive layer side surface that is the work pasting surface opposite to the surface. Specifically, for example, it is preferable to achieve both the above-described visibility of the marking information by laser marking in the laser mark layer and the work adhesiveness on the surface of the adhesive layer. In addition, when this dicing tape-integrated adhesive sheet is used in a blade dicing process in a form in which a wafer is bonded to the adhesive sheet side, the wafer cut surface is caused by impact or friction during cutting with a dicing blade. That is, from the viewpoint of suppressing cracks that may be formed on the side surface of the chip, it is preferable that the value of the ratio is larger. On the other hand, when the dicing tape-integrated adhesive sheet is used in the expanding process for cleaving described below in a form in which a wafer is bonded to the adhesive sheet side, from the viewpoint of realizing good cleaving property of the adhesive sheet. The ratio value is preferably smaller.

It is a cross-sectional schematic diagram of the dicing tape integrated adhesive sheet which concerns on one Embodiment of this invention. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used. FIG. 2 shows some steps in a semiconductor device manufacturing method in which the dicing tape-integrated adhesive sheet shown in FIG. 1 is used.

  FIG. 1 is a schematic cross-sectional view of a dicing tape-integrated adhesive sheet X according to an embodiment of the present invention. The dicing tape-integrated adhesive sheet X can be used in the manufacturing process of a semiconductor device, and has a laminated structure including a film 10 as an adhesive sheet and a dicing tape 20. In this embodiment, the film 10 is a back surface protective film to be bonded to a non-circuit-formed surface such as a semiconductor wafer as a workpiece, that is, the back surface. The dicing tape 20 has a laminated structure including a base material 21 and an adhesive layer 22. The adhesive layer 22 has an adhesive surface 22a on the film 10 side. The film 10 is in close contact with the pressure-sensitive adhesive layer 22 or the pressure-sensitive adhesive surface 22a so as to be peelable. The dicing tape-integrated adhesive sheet X has a disk shape having a size corresponding to a semiconductor wafer or the like that is a workpiece. Such a dicing tape-integrated adhesive sheet X is specifically used as a dicing tape-integrated back surface protective film in the process of obtaining a semiconductor chip with an adhesive film of a size equivalent to a chip for protecting the back surface of a semiconductor chip. It can be done.

  The film 10 which is a back surface protective film has a laminated structure including a laser mark layer 11 and an adhesive layer 12. The laser mark layer 11 is located on the dicing tape 20 side in the film 10 and is in close contact with the dicing tape 20 or its adhesive layer 22. Laser marking is applied to the surface of the laser mark layer 11 on the dicing tape 20 side in the manufacturing process of the semiconductor device. In the present embodiment, the laser mark layer 11 is a thermosetting layer containing a thermosetting component and is already thermoset. The adhesive layer 12 is located on the side of the film 10 where a workpiece such as a semiconductor wafer is bonded, and is a thermoplastic adhesive layer in this embodiment.

  The laser mark layer 11 in the film 10 may have a composition containing a thermosetting resin and a thermoplastic resin as a resin component, and is accompanied by a thermosetting functional group that can react with a curing agent to form a bond. You may have a composition containing a thermoplastic resin.

  Examples of the thermosetting resin when the laser mark layer 11 has a composition including a thermosetting resin and a thermoplastic resin include, for example, epoxy resins, phenol resins, amino resins, unsaturated polyester resins, polyurethane resins, and silicone resins. And thermosetting polyimide resin. The laser mark layer 11 may contain one type of thermosetting resin, or may contain two or more types of thermosetting resins. Since the epoxy resin tends to have a low content of ionic impurities or the like that can cause corrosion of the semiconductor chip to be protected by the back surface protection film formed from the film 10 as described later, the laser mark of the film 10 It is preferable as the thermosetting resin in the layer 11. Moreover, as a hardening | curing agent for making an epoxy resin express thermosetting, a phenol resin is preferable.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and biphenyl type epoxy. Bifunctional and polyfunctional resins such as resins, naphthalene type epoxy resins, fluorene type epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, and tetraphenylolethane type epoxy resins An epoxy resin is mentioned. Examples of the epoxy resin include hydantoin type epoxy resin, trisglycidyl isocyanurate type epoxy resin, and glycidylamine type epoxy resin. Moreover, the laser mark layer 11 may contain one type of epoxy resin, or may contain two or more types of epoxy resins.

  The phenol resin acts as a curing agent for the epoxy resin. Examples of such a phenol resin include novolaks such as a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tert-butylphenol novolak resin, and a nonylphenol novolak resin. Type phenolic resin. In addition, examples of the phenol resin include resol type phenol resins and polyoxystyrene such as polyparaoxystyrene. Particularly preferred as the phenol resin in the laser mark layer 11 is a phenol novolac resin or a phenol aralkyl resin. The laser mark layer 11 may contain one type of phenol resin or two or more types of phenol resins as a curing agent for the epoxy resin.

  When the laser mark layer 11 contains an epoxy resin and a phenol resin as its curing agent, the hydroxyl group in the phenol resin is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin. Preferably, both resins are blended at a ratio of 0.8 to 1.2 equivalents. Such a configuration is preferable in sufficiently curing the curing reaction of the epoxy resin and the phenol resin when the laser mark layer 11 is cured.

  The content of the thermosetting resin in the laser mark layer 11 is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, from the viewpoint of appropriately curing the laser mark layer 11.

  The thermoplastic resin in the laser mark layer 11 has, for example, a binder function. As the thermoplastic resin in the case where the laser mark layer 11 has a composition including a thermosetting resin and a thermoplastic resin, for example, an acrylic resin is used. Resin, natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, 6 -Polyamide resins such as nylon and 6,6-nylon, phenoxy resins, saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamideimide resins, and fluorine resins. The laser mark layer 11 may contain one type of thermoplastic resin or may contain two or more types of thermoplastic resins. The acrylic resin is preferable as the thermoplastic resin in the laser mark layer 11 because it has few ionic impurities and high heat resistance.

  When the laser mark layer 11 contains an acrylic resin as a thermoplastic resin, the acrylic resin preferably contains the largest amount of monomer units derived from (meth) acrylic acid esters by mass ratio. “(Meth) acryl” means “acryl” and / or “methacryl”.

  Examples of (meth) acrylic acid ester for forming an acrylic resin monomer unit, that is, (meth) acrylic acid ester that is a constituent monomer of acrylic resin, include (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclohexane. Examples include alkyl esters and (meth) acrylic acid aryl esters. Examples of (meth) acrylic acid alkyl esters include (meth) acrylic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Pentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester (ie lauryl ester), tridecyl ester, tetradecyl ester , Hexadecyl ester, octadecyl ester, and eicosyl ester. Examples of (meth) acrylic acid cycloalkyl ester include cyclopentyl ester and cyclohexyl ester of (meth) acrylic acid. Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylate and benzyl (meth) acrylate. As a constituent monomer of the acrylic resin, one kind of (meth) acrylic acid ester may be used, or two or more kinds of (meth) acrylic acid esters may be used. The acrylic resin can be obtained by polymerizing raw material monomers for forming the acrylic resin. Examples of the polymerization technique include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization.

  The acrylic resin may contain, as a constituent monomer, one or two or more other monomers copolymerizable with (meth) acrylic acid ester, for example, in order to improve cohesive strength and heat resistance. Examples of such monomers include carboxy group-containing monomers, acid anhydride monomers, hydroxy group-containing monomers, epoxy group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, acrylamide, and acrylonitrile. Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride. Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, ( Examples include 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, and (meth) acryloyloxynaphthalene sulfonic acid. Can be mentioned. Examples of the phosphate group-containing monomer include 2-hydroxyethyl acryloyl phosphate.

  From the viewpoint of ensuring good laser marking properties in the laser mark layer 11, the acrylic resin contained in the laser mark layer 11 is preferably butyl acrylate, ethyl acrylate, acrylonitrile, acrylic acid, 2-ethylhexyl acrylate. And a copolymer of monomers appropriately selected from glycidyl acrylate.

  When the laser mark layer 11 has a composition including a thermoplastic resin with a thermosetting functional group, for example, a thermosetting functional group-containing acrylic resin can be used as the thermoplastic resin. The acrylic resin for forming the thermosetting functional group-containing acrylic resin preferably contains the largest amount of monomer units derived from (meth) acrylic acid ester by mass ratio. As such (meth) acrylic acid ester, for example, the same (meth) acrylic acid ester as described above as the constituent monomer of the acrylic resin contained in the laser mark layer 11 can be used. The acrylic resin for forming the thermosetting functional group-containing acrylic resin is, for example, one type or two or more types copolymerizable with (meth) acrylic acid ester in order to improve the cohesive strength and heat resistance. Monomer units derived from these monomers may also be included. As such a monomer, for example, those described above as other monomers copolymerizable with (meth) acrylic acid ester for forming an acrylic resin in the laser mark layer 11 can be used. On the other hand, examples of the thermosetting functional group for forming the thermosetting functional group-containing acrylic resin include a glycidyl group, a carboxy group, a hydroxy group, and an isocyanate group. Of these, a glycidyl group and a carboxy group can be preferably used. That is, as the thermosetting functional group-containing acrylic resin, a glycidyl group-containing acrylic resin or a carboxy group-containing acrylic resin can be suitably used. Moreover, the hardening | curing agent which can produce a reaction with it according to the kind of thermosetting functional group in a thermosetting functional group containing acrylic resin is selected. When the thermosetting functional group of the thermosetting functional group-containing acrylic resin is a glycidyl group, as the curing agent, the same phenol resin as described above as the curing agent for epoxy resin can be used.

  The composition for forming the laser mark layer 11 preferably contains a thermosetting catalyst. Incorporation of a thermosetting catalyst into the composition for forming a laser mark layer is preferable in sufficiently curing the resin component in curing the laser mark layer 11 and increasing the curing reaction rate. Examples of such a thermosetting catalyst include imidazole compounds, triphenylphosphine compounds, amine compounds, and trihalogen borane compounds. Examples of imidazole compounds include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazo Lithium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- -[2'-Methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole Is mentioned. Examples of triphenylphosphine compounds include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, diphenyltolylphosphine, tetraphenylphosphonium bromide, methyltriphenylphosphonium. Methyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium, and benzyltriphenylphosphonium chloride. The triphenylphosphine compound includes a compound having both a triphenylphosphine structure and a triphenylborane structure. Such compounds include, for example, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-triborate, benzyltriphenylphosphonium tetraphenylborate, and triphenylphosphine triphenylborane. Examples of the amine compound include monoethanolamine trifluoroborate and dicyandiamide. An example of the trihalogen borane compound is trichloroborane. The composition for forming a laser mark layer may contain one type of thermosetting catalyst, or may contain two or more types of thermosetting catalysts.

  The laser mark layer 11 may contain a filler. The blending of the filler into the laser mark layer 11 is preferable in adjusting physical properties such as the elastic modulus of the laser mark layer 11, the yield point strength, and the breaking elongation. Examples of the filler include inorganic fillers and organic fillers. As a constituent material of the inorganic filler, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, nitriding Examples include boron, crystalline silica, and amorphous silica. Examples of the constituent material of the inorganic filler include simple metals such as aluminum, gold, silver, copper, and nickel, alloys, amorphous carbon, and graphite. Examples of the constituent material of the organic filler include polymethyl methacrylate (PMMA), polyimide, polyamide imide, polyether ether ketone, polyether imide, and polyester imide. The laser mark layer 11 may contain one type of filler or two or more types of filler. The filler may have various shapes such as a spherical shape, a needle shape, and a flake shape. When the laser mark layer 11 contains a filler, the average particle diameter of the filler is preferably 0.03 to 5 μm, more preferably 0.04 to 3 μm, and more preferably 0.05 to 1 μm. That is, the laser mark layer 11 preferably contains a nanofiller. The configuration in which the laser mark layer 11 contains nanofillers having such particle diameters as fillers is suitable for ensuring high fragmentation and high cleaving properties for the film 10 to be fragmented. The average particle size of the filler can be determined using, for example, a photometric particle size distribution meter (trade name “LA-910”, manufactured by Horiba, Ltd.). Further, when the laser mark layer 11 contains a filler, the content of the filler is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more. The content is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 43% by mass or less.

  The laser mark layer 11 contains a colorant in this embodiment. The colorant may be a pigment or a dye. Examples of the colorant include black colorants, cyan colorants, magenta colorants, and yellow colorants. In order to realize high visibility of information stamped on the laser mark layer 11 by laser marking, the laser mark layer 11 preferably contains a black colorant. Examples of black colorants include azo pigments such as carbon black, graphite (graphite), copper oxide, manganese dioxide, azomethine azo black, aniline black, perylene black, titanium black, cyanine black, activated carbon, ferrite, magnetite, and oxidation. Examples thereof include chromium, iron oxide, molybdenum disulfide, complex oxide black pigment, anthraquinone organic black dye, and azo organic black dye. Examples of carbon black include furnace black, channel black, acetylene black, thermal black, and lamp black. Examples of black colorants include CI Solvent Black 3, 7, 22, 22, 27, 34, 43, and 70. Examples of the black colorant include CI Direct Black 17, 19, 19, 22, 32, 38, 51, and 71. Examples of black colorants include CI Acid Black 1, 2, 24, 26, 31, 48, 52, 107, 109, 110, 119, and 154. It is done. Examples of black colorants include CI Disperse Black 1, 3, 10, and 24. Examples of the black colorant include CI Pigment Black 1 and 7. The laser mark layer 11 may contain one type of colorant or two or more types of colorant. Further, the content of the colorant in the laser mark layer 11 is preferably 0.5% by weight or more, more preferably 1% by weight or more, and more preferably 2% by weight or more. The content is preferably 10% by weight or less, more preferably 8% by weight or less, and more preferably 6% by weight or less. These configurations relating to the colorant content are preferable for realizing high visibility of information stamped on the laser mark layer 11 by laser marking.

  The laser mark layer 11 may contain one type or two or more types of other components as necessary. Examples of the other components include a flame retardant, a silane coupling agent, and an ion trap agent. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Examples of the ion trapping agent include hydrotalcites, bismuth hydroxide, hydrous antimony (eg, “IXE-300” manufactured by Toa Gosei Co., Ltd.), and zirconium phosphate having a specific structure (eg, “ IXE-100 "), magnesium silicate (for example," Kyoward 600 "manufactured by Kyowa Chemical Industry Co., Ltd.), and aluminum silicate (for example," Kyoword 700 "manufactured by Kyowa Chemical Industry Co., Ltd.) A compound capable of forming a complex with a metal ion can also be used as an ion trapping agent. Examples of such compounds include triazole compounds, tetrazole compounds, and bipyridyl compounds. Among these, a triazole compound is preferable from the viewpoint of the stability of a complex formed with a metal ion. Examples of such triazole compounds include 1,2,3-benzotriazole, 1- {N, N-bis (2-ethylhexyl) aminomethyl} benzotriazole, carboxybenzotriazole, 2- (2-hydroxy- 5-Methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) ) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 6- (2 -Benzotriazolyl) -4-t-octyl-6'-t-butyl-4'-methyl-2,2'-methylenebisphenol, 1- (2,3-dihydroxypropyl) benzotriazole, 1- (1 , 2-Dicarboxydiethyl) ben Triazole, 1- (2-ethylhexylaminomethyl) benzotriazole, 2,4-di-t-pentyl-6-{(H-benzotriazol-1-yl) methyl} phenol, 2- (2-hydroxy-5- t-butylphenyl) -2H-benzotriazole, octyl-3- [3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl- 3- [3-t-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- (2H-benzotriazol-2-yl) -6- (1 -Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4-tert-butylphenol, 2- (2- Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-o Tylphenyl) -benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzo Triazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and methyl-3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxy Phenyl] propionate. In addition, a predetermined hydroxyl group-containing compound such as a quinol compound, a hydroxyanthraquinone compound, or a polyphenol compound can also be used as an ion trapping agent. Specific examples of such a hydroxyl group-containing compound include 1,2-benzenediol, alizarin, anthralphine, tannin, gallic acid, methyl gallate, and pyrogallol.

  The adhesive layer 12 in the film 10 may have a composition including a thermosetting resin and a thermoplastic resin as a resin component, and is accompanied by a thermosetting functional group that can react with the curing agent to form a bond. You may have a composition containing a thermoplastic resin.

  Examples of the thermosetting resin when the adhesive layer 12 has a composition including a thermosetting resin and a thermoplastic resin include, for example, epoxy resins, phenol resins, amino resins, unsaturated polyester resins, polyurethane resins, and silicone resins. And thermosetting polyimide resin. The adhesive layer 12 may contain one type of thermosetting resin, or may contain two or more types of thermosetting resins. Since the epoxy resin tends to have a low content of ionic impurities and the like that can cause corrosion of the semiconductor chip that is the target of protection by the back surface protection film formed from the film 10 as described later, the adhesive of the film 10 Preferred as a thermosetting resin in layer 12.

  As an epoxy resin in the adhesive bond layer 12, what was mentioned above as an epoxy resin which is the said thermosetting resin in case the laser mark layer 11 has a composition containing a thermosetting resin and a thermoplastic resin is mentioned, for example. Phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, trishydroxyphenylmethane type epoxy resin, and tetraphenylol ethane type epoxy resin are rich in reactivity with phenol resin as curing agent and heat resistant Since it is excellent in property, it is preferable as an epoxy resin in the adhesive layer 12.

  Examples of the phenol resin that can act as a curing agent for the epoxy resin in the adhesive layer 12 include those described above as a phenol resin that is a curing agent for the epoxy resin in the laser mark layer 11. The adhesive layer 12 may contain one type of phenol resin or two or more types of phenol resins as a curing agent for the epoxy resin.

  When the adhesive layer 12 contains an epoxy resin and a phenol resin as its curing agent, the hydroxyl group in the phenol resin is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin. Preferably, both resins are blended at a ratio of 0.8 to 1.2 equivalents.

  The content ratio of the thermosetting resin in the adhesive layer 12 is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, from the viewpoint of ensuring the adhesiveness of the adhesive layer 12 to a workpiece such as a semiconductor wafer. It is.

  The thermoplastic resin in the adhesive layer 12 has a binder function, for example. As the said thermoplastic resin in case the adhesive bond layer 12 has a composition containing a thermosetting resin and a thermoplastic resin, for example, when the laser mark layer 11 has a composition containing a thermosetting resin and a thermoplastic resin Examples of the thermoplastic resin include those described above. The adhesive layer 12 may contain one type of thermoplastic resin or may contain two or more types of thermoplastic resins. The acrylic resin is preferable as the thermoplastic resin in the adhesive layer 12 because it has few ionic impurities and high heat resistance.

  When the adhesive layer 12 contains an acrylic resin as a thermoplastic resin, the acrylic resin preferably contains the largest amount of monomer units derived from (meth) acrylic acid esters by mass ratio. As the (meth) acrylic acid ester for forming such a monomer unit of acrylic resin, for example, the above-mentioned monomer constituting the acrylic resin when the laser mark layer 11 contains an acrylic resin as a thermoplastic resin (meth ) Acrylic acid esters can be used. As a constituent monomer of the acrylic resin in the adhesive layer 12, one type of (meth) acrylic acid ester may be used, or two or more types of (meth) acrylic acid ester may be used. In addition, the acrylic resin may contain, as a constituent monomer, one or two or more other monomers copolymerizable with (meth) acrylic acid ester, for example, in order to improve cohesion and heat resistance. As such a monomer, for example, those described above as other monomers copolymerizable with (meth) acrylic acid ester for forming an acrylic resin in the laser mark layer 11 can be used.

  From the viewpoint of ensuring the adhesiveness of the adhesive layer 12 to a workpiece such as a semiconductor wafer, the acrylic resin contained in the adhesive layer 12 is preferably butyl acrylate, ethyl acrylate, acrylonitrile, acrylic acid, acrylic acid 2 -Copolymer of monomers appropriately selected from ethylhexyl and glycidyl acrylate.

  When the adhesive layer 12 has a composition including a thermoplastic resin with a thermosetting functional group, for example, a thermosetting functional group-containing acrylic resin can be used as the thermoplastic resin. The acrylic resin for forming the thermosetting functional group-containing acrylic resin preferably contains the largest amount of monomer units derived from (meth) acrylic acid ester by mass ratio. As such (meth) acrylic acid ester, for example, the same (meth) acrylic acid ester as described above as the constituent monomer of the acrylic resin contained in the laser mark layer 11 can be used. The acrylic resin for forming the thermosetting functional group-containing acrylic resin is, for example, one type or two or more types copolymerizable with (meth) acrylic acid ester in order to improve the cohesive strength and heat resistance. Monomer units derived from these monomers may also be included. As such a monomer, for example, those described above as other monomers copolymerizable with (meth) acrylic acid ester for forming an acrylic resin in the laser mark layer 11 can be used. On the other hand, examples of the thermosetting functional group for forming the thermosetting functional group-containing acrylic resin include a glycidyl group, a carboxy group, a hydroxy group, and an isocyanate group. Of these, a glycidyl group and a carboxy group can be preferably used. Moreover, the hardening | curing agent which can produce a reaction with it according to the kind of thermosetting functional group in a thermosetting functional group containing acrylic resin is selected. When the thermosetting functional group of the thermosetting functional group-containing acrylic resin is a glycidyl group, as the curing agent, the same phenol resin as described above as the curing agent for epoxy resin can be used.

  The composition for forming the adhesive layer 12 preferably does not contain a thermosetting catalyst. When a thermosetting catalyst is blended in the composition for forming the adhesive layer 12, for example, the above-described thermosetting catalyst that can be blended in the laser mark layer forming composition is used. be able to.

  The adhesive layer 12 may contain a filler. The blending of the filler into the adhesive layer 12 is preferable in adjusting physical properties such as the elastic modulus, yield strength, and elongation at break of the adhesive layer 12. Examples of the filler in the adhesive layer 12 include those described above as the filler in the laser mark layer 11. The adhesive layer 12 may contain one type of filler, or may contain two or more types of fillers. The filler may have various shapes such as a spherical shape, a needle shape, and a flake shape. When the adhesive layer 12 contains a filler, the average particle diameter of the filler is preferably 0.03 to 5 μm, more preferably 0.04 to 3 μm, and more preferably 0.05 to 1 μm. That is, the adhesive layer 12 preferably contains a nanofiller. The configuration in which the adhesive layer 12 contains nanofillers having such particle diameters as fillers avoids damage caused by the filler contained in the adhesive layer 12 on the workpiece adhered or mounted on the film 10. Or it is suitable when suppressing, and it is suitable when ensuring high parting property and high cleaving property about the film 10 to be fragmented. Moreover, content of the said filler in case the adhesive bond layer 12 contains a filler becomes like this. Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more. The content is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 43% by mass or less.

  The adhesive layer 12 may contain a colorant. Examples of the colorant in the adhesive layer 12 include those described above as the colorant in the laser mark layer 11. In order to ensure high contrast between a marking portion by laser marking on the laser mark layer 11 side of the film 10 and a portion other than that to realize high visibility of the marking information, the adhesive layer 12 is colored black. It is preferable to contain an agent. The adhesive layer 12 may contain one type of colorant, or may contain two or more types of colorants. Further, the content of the colorant in the adhesive layer 12 is preferably 0.5% by weight or more, more preferably 1% by weight or more, and more preferably 2% by weight or more. The content is preferably 10% by weight or less, more preferably 8% by weight or less, and more preferably 6% by weight or less. These configurations relating to the colorant content are preferable for realizing the above-described high visibility of the marking information by laser marking.

  The adhesive layer 12 may contain one kind or two or more kinds of other components as necessary. Examples of the other components include a flame retardant, a silane coupling agent, and an ion trap agent specifically described above with respect to the laser mark layer 11.

  The thickness of the film 10 having a laminated structure including the laser mark layer 11 and the adhesive layer 12 is preferably 8 μm or more, more preferably 10 μm or more, and preferably 30 μm or less, more preferably 25 μm or less. The ratio of the thickness of the laser mark layer 11 to the thickness of the adhesive layer 12 is preferably 0.65 to 12, more preferably 0.75 to 7.5, and more preferably 0.85 to 5. .5.

  The substrate 21 of the dicing tape 20 in the dicing tape integrated adhesive sheet X is an element that functions as a support in the dicing tape 20 or the dicing tape integrated adhesive sheet X. The substrate 21 is, for example, a plastic substrate, and a plastic film can be suitably used as the plastic substrate. For example, polyolefin, polyester, polyurethane, polycarbonate, polyether ether ketone, polyimide, polyether imide, polyamide, wholly aromatic polyamide, polyvinyl chloride, polyvinylidene chloride, polyphenyl sulfide, aramid , Fluororesin, cellulosic resin, and silicone resin. Examples of the polyolefin include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, Examples include ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-butene copolymer, and ethylene-hexene copolymer. It is done. Examples of the polyester include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. The base material 21 may be made of one kind of material or may be made of two or more kinds of materials. The base material 21 may have a single layer structure or a multilayer structure. When the pressure-sensitive adhesive layer 22 on the substrate 21 is ultraviolet curable as described later, the substrate 21 preferably has ultraviolet transparency. When the base material 21 is made of a plastic film, it may be an unstretched film, a uniaxially stretched film, or a biaxially stretched film. In the present embodiment, the base material 21 is preferably a polyvinyl chloride base material or an ethylene-vinyl acetate copolymer base material.

  When the dicing tape 20 or the base material 21 is shrunk by, for example, partial heating when using the dicing tape-integrated adhesive sheet X, the base material 21 preferably has heat shrinkability. Moreover, when the base material 21 consists of a plastic film, in order to implement | achieve isotropic heat-shrinkability about the dicing tape 20 thru | or the base material 21, it is preferable that the base material 21 is a biaxially stretched film. The dicing tape 20 to the base material 21 preferably have a heat shrinkage rate of 2 to 30%, more preferably 2 to 25%, more preferably a heat treatment test performed under conditions of a heating temperature of 100 ° C. and a heat treatment time of 60 seconds. 3 to 20%, more preferably 5 to 20%. The heat shrinkage rate means a heat shrinkage rate of at least one of a so-called MD direction heat shrinkage rate and a so-called TD direction heat shrinkage rate.

  The surface on the pressure-sensitive adhesive layer 22 side of the base material 21 may be subjected to physical treatment, chemical treatment, or undercoating treatment for enhancing the adhesion with the pressure-sensitive adhesive layer 22. Examples of the physical treatment include corona treatment, plasma treatment, sand mat processing treatment, ozone exposure treatment, flame exposure treatment, high piezoelectric impact exposure treatment, and ionizing radiation treatment. Examples of chemical treatment include chromic acid treatment.

  The thickness of the base material 21 is preferably 40 μm or more, preferably 50 μm or more from the viewpoint of ensuring the strength required for the base material 21 to function as a support in the dicing tape 20 or the dicing tape integrated adhesive sheet X. More preferably, it is 60 μm or more. Further, from the viewpoint of realizing appropriate flexibility in the dicing tape 20 or the dicing tape integrated adhesive sheet X, the thickness of the base material 21 is preferably 200 μm or less, more preferably 180 μm or less, more preferably 150 μm or less.

  The pressure-sensitive adhesive layer 22 of the dicing tape 20 contains a pressure-sensitive adhesive (radiation-curable pressure-sensitive adhesive) that can be cured by irradiation in the course of use of the dicing tape-integrated adhesive sheet X and has radiation curability. In the pressure-sensitive adhesive layer 22 of the present embodiment, one type of radiation curable pressure sensitive adhesive may be used, or two or more types of radiation curable pressure sensitive adhesive may be used. Moreover, the whole adhesive layer 22 may be formed from a radiation curable adhesive, and a part of adhesive layer 22 may be formed from a radiation curable adhesive. For example, when the pressure-sensitive adhesive layer 22 has a single-layer structure, the whole pressure-sensitive adhesive layer 22 may be formed from a radiation-curable pressure-sensitive adhesive, or a predetermined part (for example, a workpiece sticking target) in the pressure-sensitive adhesive layer 22 The central region which is the region) is formed from the radiation curable adhesive, and the other part (for example, the region to be attached to the ring frame and outside the central region) is formed from the radiation curable adhesive. May be. Further, when the pressure-sensitive adhesive layer 22 has a multilayer structure, all the layers forming the multilayer structure may be formed of a radiation-curable pressure-sensitive adhesive, or at least a part of the layers including the surface layer on the film 10 side in the multilayer structure. You may form from a radiation curable adhesive.

  Examples of the radiation curable pressure sensitive adhesive for the pressure sensitive adhesive layer 22 include a type of pressure sensitive adhesive that is cured by irradiation with electron beams, ultraviolet rays, α rays, β rays, γ rays, or X rays. A curable pressure sensitive adhesive (ultraviolet curable pressure sensitive adhesive) can be used particularly preferably.

  Examples of the radiation-curable pressure-sensitive adhesive for the pressure-sensitive adhesive layer 22 include a base polymer such as an acrylic polymer that is an acrylic pressure-sensitive adhesive, and radiation-polymerizable having a functional group such as a radiation-polymerizable carbon-carbon double bond. Addition-type radiation-curable pressure-sensitive adhesives containing the monomer component and oligomer component are mentioned.

  The acrylic polymer preferably contains the largest amount of monomer units derived from (meth) acrylic acid ester in mass ratio. Examples of (meth) acrylic acid esters for forming monomer units of acrylic polymers, that is, (meth) acrylic acid esters that are constituent monomers of acrylic polymers include, for example, (meth) acrylic acid alkyl esters, (meth) acrylic esters Acid cycloalkyl esters and (meth) acrylic acid aryl esters, and more specifically, (meth) acrylic esters similar to those described above with respect to the acrylic resin in the laser mark layer 11 of the film 10. As a constituent monomer of the acrylic polymer, one kind of (meth) acrylic acid ester may be used, or two or more kinds of (meth) acrylic acid esters may be used. The constituent monomer of the acrylic polymer preferably includes 2-ethylhexyl acrylate and lauryl acrylate. Further, in order to appropriately express the basic characteristics such as adhesiveness due to (meth) acrylic acid ester in the pressure-sensitive adhesive layer 22, the ratio of (meth) acrylic acid ester to the whole monomer constituting the acrylic polymer is preferably It is 40 mass% or more, More preferably, it is 60 mass% or more.

  Acrylic polymers contain monomer units derived from one or more other monomers copolymerizable with (meth) acrylic acid esters, for example, to modify their cohesive strength and heat resistance. Also good. Examples of such monomers include carboxy group-containing monomers, acid anhydride monomers, hydroxy group-containing monomers, epoxy group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, acrylamide, and acrylonitrile, and more Specifically, those mentioned above as other monomers copolymerizable with a (meth) acrylic acid ester for forming an acrylic resin in the laser mark layer 11 of the film 10 may be mentioned.

  The acrylic polymer may contain a monomer unit derived from a polyfunctional monomer copolymerizable with a monomer component such as (meth) acrylic acid ester in order to form a crosslinked structure in the polymer skeleton. Examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyglycidyl (meth) acrylate, polyester (meth) acrylate, and urethane ( And (meth) acrylate. “(Meth) acrylate” shall mean “acrylate” and / or “methacrylate”. As a constituent monomer of the acrylic polymer, one kind of polyfunctional monomer may be used, or two or more kinds of polyfunctional monomers may be used. In order to appropriately develop basic characteristics such as adhesiveness due to (meth) acrylic acid ester in the pressure-sensitive adhesive layer 22, the ratio of the polyfunctional monomer in the entire constituent monomers of the acrylic polymer is preferably 40% by mass or less. , Preferably it is 30 mass% or less.

  The acrylic polymer can be obtained by polymerizing raw material monomers for forming the acrylic polymer. Examples of the polymerization technique include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. From the viewpoint of high cleanliness in the semiconductor device manufacturing method in which the dicing tape 20 or the dicing tape integrated adhesive sheet X is used, the dicing tape 20 or the dicing tape integrated adhesive sheet X in the pressure-sensitive adhesive layer 22 is low. Where the molecular weight substance is preferably small, the number average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 200,000 to 3,000,000.

  The pressure-sensitive adhesive layer 22 or the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer 22 may contain, for example, an external crosslinking agent in order to increase the number average molecular weight of the base polymer such as an acrylic polymer. Examples of the external crosslinking agent for reacting with a base polymer such as an acrylic polymer to form a crosslinked structure include polyisocyanate compounds, epoxy compounds, polyol compounds, aziridine compounds, and melamine crosslinking agents. The content of the external crosslinking agent in the pressure-sensitive adhesive layer 22 or the pressure-sensitive adhesive forming the same is preferably 5 parts by mass or less, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the base polymer.

  Examples of the radiation-polymerizable monomer component for forming the radiation-curable pressure-sensitive adhesive include urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth). Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4-butanediol di (meth) acrylate. Examples of the radiation-polymerizable oligomer component for forming the radiation-curable pressure-sensitive adhesive include various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based, having a molecular weight of about 100 to 30000. Things are appropriate. The total content of the radiation-polymerizable monomer component and oligomer component in the radiation-curable pressure-sensitive adhesive is determined within a range in which the adhesive strength of the pressure-sensitive adhesive layer 22 to be formed can be appropriately reduced. Preferably it is 5-500 mass parts with respect to 100 mass parts, More preferably, it is 40-150 mass parts. Further, as the additive type radiation curable pressure-sensitive adhesive, for example, those disclosed in JP-A-60-196956 may be used.

  Examples of the radiation-curable pressure-sensitive adhesive for the pressure-sensitive adhesive layer 22 include, for example, a base polymer having a functional group such as a radiation-polymerizable carbon-carbon double bond at the polymer side chain or at the polymer main chain terminal in the polymer main chain. Intrinsic radiation-curable pressure-sensitive adhesives containing Such an internal radiation curable pressure-sensitive adhesive is suitable for suppressing an unintended change in the pressure-sensitive adhesive property due to movement of a low molecular weight component in the pressure-sensitive adhesive layer 22 to be formed.

  As the base polymer contained in the internal radiation-curable pressure-sensitive adhesive, those having an acrylic polymer as a basic skeleton are preferable. As the acrylic polymer having such a basic skeleton, the above-mentioned acrylic polymer can be employed. As a method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer, for example, a raw material monomer including a monomer having a predetermined functional group (first functional group) is copolymerized to form an acrylic polymer. After obtaining, a compound having a predetermined functional group (second functional group) that can react and bond with the first functional group and a radiation-polymerizable carbon-carbon double bond is converted to carbon-carbon. Examples thereof include a method of subjecting an acrylic polymer to a condensation reaction or an addition reaction while maintaining the radiation polymerization property of a double bond.

  Examples of the combination of the first functional group and the second functional group include, for example, carboxy group and epoxy group, epoxy group and carboxy group, carboxy group and aziridyl group, aziridyl group and carboxy group, hydroxy group and isocyanate group, and isocyanate group. And a hydroxy group. Of these combinations, a combination of a hydroxy group and an isocyanate group or a combination of an isocyanate group and a hydroxy group is preferable from the viewpoint of easy reaction tracking. In addition, since it is technically difficult to prepare a polymer having a highly reactive isocyanate group, from the viewpoint of easy preparation or availability of the acrylic polymer, the first functional group on the acrylic polymer side is used. More preferably, the group is a hydroxy group and the 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, that is, a radiation-polymerizable unsaturated functional group-containing isocyanate compound, for example, methacryloyl isocyanate, 2 -Methacryloyloxyethyl isocyanate (MOI) and m-isopropenyl-α, α-dimethylbenzyl isocyanate.

  The radiation curable pressure sensitive adhesive for the pressure sensitive adhesive layer 22 preferably contains a photopolymerization initiator. Examples of photopolymerization initiators include α-ketol compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, camphors. Examples include quinones, halogenated ketones, acyl phosphinoxides, and acyl phosphonates. Examples of α-ketol compounds include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypro Piophenone and 1-hydroxycyclohexyl phenyl ketone are mentioned. Examples of acetophenone compounds include methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxyacetophenone, and 2-methyl-1- [4- (methylthio)- Phenyl] -2-morpholinopropane-1. Examples of benzoin ether compounds include benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether. Examples of the ketal compound include benzyl dimethyl ketal. Examples of the aromatic sulfonyl chloride compound include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime compound include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. Examples of the benzophenone-based compound include benzophenone, benzoylbenzoic acid, and 3,3′-dimethyl-4-methoxybenzophenone. Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropyl. Thioxanthone is mentioned. The content of the photopolymerization initiator in the radiation-curable pressure-sensitive adhesive in the pressure-sensitive adhesive layer 22 is, for example, 0.05 to 20 parts by mass with respect to 100 parts by mass of the base polymer such as an acrylic polymer.

  The pressure-sensitive adhesive layer 22 or the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer may contain, in addition to the above-described components, a crosslinking accelerator, a tackifier, an anti-aging agent, a colorant such as a pigment or a dye, and the like. The colorant may be a compound that is colored by irradiation. Examples of such a compound include leuco dyes.

  The thickness of the pressure-sensitive adhesive layer 22 is preferably 2 to 40 μm, more preferably 3 to 30 μm, and more preferably 4 to 20 μm. Such a configuration is suitable, for example, when the pressure-sensitive adhesive layer 22 contains a radiation-curable pressure-sensitive adhesive and balances the pressure-sensitive adhesive force on the film 10 before and after the radiation curing of the pressure-sensitive adhesive layer 22.

In the film 10 of the dicing tape-integrated adhesive sheet X, the surface 11a on the laser mark layer side is 0. 0 in a peel test at 23 ° C, a peel angle of 180 °, and a tensile speed of 300 mm / min. The peel adhesive strength is 2 N / 10 mm or less, preferably 0.1 N / 10 mm or less, more preferably 0.07 N / 10 mm or less. Specifically, the preparation method and the measurement method of the test piece used for the measurement are as follows. First, in the dicing tape-integrated adhesive sheet X, the pressure-sensitive adhesive layer 22 is cured by irradiating the pressure-sensitive adhesive layer 22 with radiation such as ultraviolet rays having an integrated irradiation light quantity of 300 mJ / cm ² from the substrate 21 side. Next, a single-sided adhesive tape (trade name “BT-315”, manufactured by Nitto Denko Corporation) is bonded to the surface 12a on the adhesive layer side of the film 10 of the dicing tape-integrated adhesive sheet X. This bonding is performed by a pressing operation in which a 2 kg hand roller is reciprocated once. Next, a laminated body having a laminated structure of the dicing tape 20, the film 10, and the single-sided adhesive tape and having a size of 10 mm wide × 100 mm long is cut out from the bonded body. Next, the dicing tape 20 is peeled from the laminate. Thereby, the test piece (width 10mm x length 100mm) which has the laminated structure of the film 10 and the single-sided adhesive tape which the surface 11a by the side of a laser mark layer is exposed is obtained. Next, after confirming that the surface temperature of a silicon wafer (diameter is, for example, 6 inches) placed on a hot plate with a set temperature of 80 ° C. is 75 ° C. or higher, the silicon wafer surface and the film on the test piece 10 and the surface 11a on the laser mark layer side are bonded together. This bonding is performed by a pressing operation in which a 2 kg hand roller is reciprocated once. Then, after standing for 2 minutes on a hot plate, using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation), 23 ° C., peeling angle 180 ° and tensile speed 300 mm. A peel test is performed under the conditions of / min, and the peel adhesion of the surface 11a on the laser mark layer side of the film 10 to the silicon wafer is measured. The adjustment of the peeling adhesive force can be performed, for example, by selecting a catalyst used in the laser mark layer 11 or adjusting a drying condition.

In the film 10 of the dicing tape-integrated adhesive sheet X, the surface 12a on the adhesive layer side is 5 N / in a peel test at 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. The peel adhesive strength is 10 mm or more, preferably 6 N / 10 mm or more, more preferably 7 N / 10 mm or more. The peel adhesive strength can be measured using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation). Specifically, the preparation method and the measurement method of the test piece used for the measurement are as follows. First, in the dicing tape integrated adhesive sheet X, the pressure-sensitive adhesive layer 22 is cured by irradiating the pressure-sensitive adhesive layer 22 with radiation such as ultraviolet rays having an integrated irradiation light amount of 300 mJ / cm ² from the base 21 side. The film 10 is peeled from the dicing tape 20 of the dicing tape-integrated adhesive sheet X. Next, a single-sided adhesive tape (trade name “BT-315”, manufactured by Nitto Denko Corporation) is bonded to the surface 11a of the peeled film 10 on the laser mark layer side. Next, a test piece having a laminated structure of the film 10 and the single-sided adhesive tape and having a size of width 10 mm × length 100 mm is cut out from the bonded body. Next, after confirming that the surface temperature of a silicon wafer (diameter is, for example, 6 inches) placed on a hot plate with a set temperature of 80 ° C. is 75 ° C. or higher, the silicon wafer surface and the film on the test piece 10 and the adhesive layer side surface 12a are bonded together. This bonding is performed by a pressing operation in which a 2 kg hand roller is reciprocated once. Then, after standing for 2 minutes on a hot plate, using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation), 23 ° C., peeling angle 180 ° and tensile speed 300 mm. A peel test is performed under the conditions of / min, and the peel adhesive strength of the surface 12a on the adhesive layer side of the film 10 to the silicon wafer is measured. The adjustment of the peeling adhesive force is performed by, for example, selecting the kind of each resin component such as acrylic resin, epoxy resin, phenol resin, and the like in the adhesive layer 12, adjusting the content, adjusting the inorganic filler content, and the like. Is possible.

In the dicing tape-integrated adhesive sheet X, the first peel adhesion in a peel test between the radiation-cured pressure-sensitive adhesive layer 22 and the film 10 under the conditions of 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. The force is 0.15 N / 20 mm or less, preferably 0.13 N / 20 mm or less, more preferably 0.09 N / 20 mm or less. The peel adhesive strength can be measured using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation). Specifically, the preparation method and the measurement method of the test piece used for the measurement are as follows. First, in the dicing tape-integrated adhesive sheet X, the pressure-sensitive adhesive layer 22 is cured by irradiating the pressure-sensitive adhesive layer 22 with radiation such as ultraviolet rays having an integrated irradiation light quantity of 300 mJ / cm ² from the substrate 21 side. Next, a single-sided adhesive tape (trade name “BT-315”, manufactured by Nitto Denko Corporation) is bonded to the surface 12 a on the adhesive layer side of the film 10 in the dicing tape-integrated adhesive sheet X. This bonding is performed by a pressing operation in which a 2 kg hand roller is reciprocated once. Next, a test piece having a width of 100 mm and a length of 100 mm having a laminated structure of the dicing tape 20, the film 10, and a single-sided adhesive tape is cut out from the bonded body. Then, using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation), the test piece was subjected to a peel test at 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. Then, the peeling adhesive force (first peeling adhesive force) between the radiation-cured adhesive layer 22 and the film 10 in the dicing tape-integrated adhesive sheet X is measured. Adjustment of this peeling adhesive force can be performed by adjusting the bonding temperature, for example.

In the dicing tape-integrated adhesive sheet X, 23 ° C., peel angle between the radiation-cured pressure-sensitive adhesive layer 22 and the film 10 after storage of the dicing tape-integrated adhesive sheet X at 50 ° C. for 9 days The difference between the second peel adhesive force and the first peel adhesive force in the peel test at 180 ° and a tensile speed of 300 mm / min is 0.12 N / 20 mm or less, preferably 0.1 N / 20 mm or less, More preferably, it is 0.07 N / 20 mm or less. The second peel adhesive strength can be measured using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation). Specifically, the preparation method and the measurement method of the test piece used for the measurement are as follows. First, the dicing tape-integrated adhesive sheet X is stored in an environment of 50 ° C. for 9 days. Next, in the dicing tape-integrated adhesive sheet X having undergone such storage, the adhesive layer 22 is irradiated with radiation such as ultraviolet rays having an integrated irradiation light amount of 300 mJ / cm ² from the substrate 21 side. 22 is cured. Next, a single-sided adhesive tape (trade name “BT-315”, manufactured by Nitto Denko Corporation) is bonded to the surface 12 a on the adhesive layer side of the film 10 in the dicing tape-integrated adhesive sheet X. This bonding is performed by a pressing operation in which a 2 kg hand roller is reciprocated once. Next, a test piece having a width of 100 mm and a length of 100 mm having a laminated structure of the film 10 and the single-sided adhesive tape is cut out from the bonded body. Then, using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation), the test piece was subjected to a peel test at 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. Then, the peel adhesive force (second peel adhesive force) between the radiation-cured pressure-sensitive adhesive layer 22 and the film 10 in the dicing tape-integrated adhesive sheet X is measured. The adjustment of the peeling adhesive force can be performed by adjusting the storage environment such as storage temperature and storage humidity.

  The dicing tape-integrated adhesive sheet X having the above-described configuration can be manufactured, for example, as follows.

  In the production of the film 10 in the dicing tape-integrated adhesive sheet X, first, a resin film (first resin film) that forms the laser mark layer 11 and a resin film (first film) that forms the adhesive layer 12. 2 resin films). The first resin film is prepared by applying a resin composition for forming a laser mark layer on a predetermined separator to form a resin composition layer, and then drying and curing the composition layer by heating. Can do. Examples of the separator include a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, and a plastic film or paper whose surface is coated with a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate release agent. Can be mentioned. Examples of the method for applying the resin composition include roll coating, screen coating, and gravure coating. In the production of the first resin film, the heating temperature is, for example, 90 to 160 ° C., and the heating time is, for example, 2 to 4 minutes. On the other hand, the second resin film is produced by applying a resin composition for forming an adhesive layer on a predetermined separator to form a resin composition layer, and then drying the composition layer by heating. Can do. In the production of the second resin film, the heating temperature is, for example, 90 to 150 ° C., and the heating time is, for example, 1 to 2 minutes. As described above, the first and second resin films described above can be produced in a form each accompanied by a separator. And the exposed surfaces of these 1st and 2nd resin films are bonded together. Thereby, the above-described film 10 having a laminated structure of the laser mark layer 11 and the adhesive layer 12 is produced.

  The dicing tape 20 of the dicing tape-integrated adhesive sheet X can be produced by providing the pressure-sensitive adhesive layer 22 on the prepared base material 21. For example, the resin base material 21 is produced by a film forming method such as a calendar film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, or a dry lamination method. can do. The film or substrate 21 after film formation is subjected to a predetermined surface treatment as necessary. In the formation of the pressure-sensitive adhesive layer 22, for example, after preparing a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer, first, the composition is applied onto the substrate 21 or a predetermined separator, and then the pressure-sensitive adhesive composition layer. Form. Examples of the method for applying the pressure-sensitive adhesive composition include roll coating, screen coating, and gravure coating. Next, the pressure-sensitive adhesive composition layer is dried by heating as necessary, and a crosslinking reaction is caused as necessary. The heating temperature is, for example, 80 to 150 ° C., and the heating time is, for example, 0.5 to 5 minutes. When the pressure-sensitive adhesive layer 22 is formed on the separator, the pressure-sensitive adhesive layer 22 with the separator is bonded to the base material 21, and then the separator is peeled off. Thereby, the above-mentioned dicing tape 20 having a laminated structure of the base material 21 and the pressure-sensitive adhesive layer 22 is produced.

In the production of the dicing tape-integrated adhesive sheet X, the laser mark layer 11 side of the film 10 is then bonded to the pressure-sensitive adhesive layer 22 side of the dicing tape 20. The bonding temperature is, for example, 20 to 50 ° C., and the bonding pressure (linear pressure) is, for example, 0.1 to 20 kgf / cm. Before the bonding, the pressure-sensitive adhesive layer 22 may be irradiated with radiation such as ultraviolet rays. After the bonding, the pressure-sensitive adhesive layer 22 is irradiated with radiation such as ultraviolet rays from the substrate 21 side. May be. Alternatively, in the process of manufacturing the dicing tape-integrated adhesive sheet X, such irradiation may not be performed (in this case, the pressure-sensitive adhesive layer 22 is radiation-cured in the process of using the dicing tape-integrated adhesive sheet X). Is possible). In the case where the pressure-sensitive adhesive layer 22 is of an ultraviolet curable type, the ultraviolet irradiation amount for curing the pressure-sensitive adhesive layer 22 is, for example, 50 to 500 mJ / cm ² . In the dicing tape-integrated adhesive sheet X, the region where the pressure-sensitive adhesive layer 22 is irradiated as a measure for reducing the adhesive strength (irradiation region R) is, for example, as shown in FIG. It is an area | region except the peripheral part in the inside.

  As described above, the dicing tape-integrated adhesive sheet X can be produced. The dicing tape integrated adhesive sheet X may be provided with a separator (not shown) on the film 10 side so as to cover at least the film 10. When the film 10 is smaller than the pressure-sensitive adhesive layer 22 of the dicing tape 20 and there is a region where the film 10 is not bonded to the pressure-sensitive adhesive layer 22, for example, the separator covers at least the film 10 and the pressure-sensitive adhesive layer 22. It may be provided in the form. The separator is an element for protecting the film 10 and the pressure-sensitive adhesive layer 22 from being exposed, and is peeled off from the film when the dicing tape-integrated adhesive sheet X is used.

  2 to 6 show an example of a semiconductor device manufacturing method in which the above-described dicing tape-integrated adhesive sheet X is used.

  In this semiconductor device manufacturing method, first, as shown in FIGS. 2A and 2B, the semiconductor wafer W is thinned by grinding (wafer thinning step). Grinding can be performed using a grinding apparatus equipped with a grinding wheel. The semiconductor wafer W has a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) are already formed on the first surface Wa side of the semiconductor wafer W, and wiring structures and the like (not shown) necessary for the semiconductor elements are already formed on the first surface Wa. Has been. The second surface Wb is a so-called back surface. In this step, after the wafer processing tape T1 having the adhesive surface T1a is bonded to the first surface Wa side of the semiconductor wafer W, the semiconductor wafer W is held in the state where the semiconductor wafer W is held on the wafer processing tape T1. The thinned semiconductor wafer 30 is obtained by grinding from the second surface Wb until a predetermined thickness is reached.

  Next, as shown in FIG. 3A, the semiconductor wafer 30 held on the wafer processing tape T1 is bonded to the film 10 of the dicing tape-integrated adhesive sheet X or the adhesive layer 12 thereof. . Thereafter, as shown in FIG. 3B, the wafer processing tape T1 is peeled off from the semiconductor wafer 30. Thereafter, baking may be performed (baking step). In the baking step, the heating temperature is, for example, 60 to 80 ° C., and the heating time is 0.5 to 2 hours. By such baking, the adhesiveness between the film 10 of the dicing tape-integrated adhesive sheet X and the semiconductor wafer 30 may be appropriately increased.

Next, laser marking is performed by irradiating the laser mark layer 11 of the film 10 in the dicing tape-integrated adhesive sheet X from the substrate 21 side of the dicing tape 20 (laser marking step). By this laser marking, various pieces of information such as character information and graphic information are given to each semiconductor element that is later separated into semiconductor chips. In this step, it is possible to efficiently and efficiently perform laser marking on a large number of semiconductor elements in the semiconductor wafer 30 in one laser marking process. Examples of the laser used in this step include a gas laser and a solid laser. Examples of the gas laser include a carbon dioxide laser (CO ₂ laser) and an excimer laser. An example of the solid laser is an Nd: YAG laser.

  Next, after the ring frame 41 is affixed on the pressure-sensitive adhesive layer 22 in the dicing tape-integrated adhesive sheet X, as shown in FIG. 4, cutting is performed with a dicing blade included in the dicing apparatus (blade dicing). Process, in FIG. 4, the cutting location is schematically represented by a thick line). In this step, the semiconductor wafer 30 is divided into semiconductor chips 31 and the dicing tape-integrated adhesive sheet X film 10 is cut into small pieces of film 10 ′. Thereby, the semiconductor chip 31 with the film 10 ′ for forming the back surface protective film, that is, the semiconductor chip 31 with film is obtained.

In the dicing tape-integrated adhesive sheet X in which the pressure-sensitive adhesive layer 22 of the dicing tape 20 has radiation curability, instead of the above-described radiation irradiation in the manufacturing process, the substrate 21 is separated after the semiconductor chip individualization step. The adhesive layer 22 may be irradiated with radiation such as ultraviolet rays from the side. The irradiation amount is, for example, 50 to 500 mJ / cm ² . In the dicing tape-integrated adhesive sheet X, an area (irradiation area R shown in FIG. 1) where irradiation is performed as a measure for reducing the adhesive strength of the pressure-sensitive adhesive layer 22 is, for example, within the film 10 bonding area in the pressure-sensitive adhesive layer 22 This is an area excluding the peripheral edge.

  Next, a cleaning process for cleaning the semiconductor chip 31 side of the dicing tape 20 with the semiconductor chip 31 with a film using a cleaning liquid such as water, and an expanding process for widening the separation distance between the semiconductor chips 31 with a film, After passing as needed, as shown in FIG. 5, the semiconductor chip 31 with a film is picked up from the dicing tape 20 (pickup process). For example, the dicing tape-integrated adhesive sheet X with the ring frame 41 is held by the holder 42 of the apparatus, and the pickup mechanism of the semiconductor chip 31 with a film to be picked up is below the dicing tape 20 in the figure. After the pin member 43 is raised and pushed up through the dicing tape 20, the pin member 43 is sucked and held by the suction jig 44. In the pickup process, the push-up speed of the pin member 43 is 1 to 100 mm / second, for example, and the push-up amount of the pin member 43 is 50 to 3000 μm, for example.

  Next, as shown in FIG. 6, the semiconductor chip with film 31 is flip-chip mounted on the mounting substrate 51. Examples of the mounting substrate 51 include a lead frame, a TAB (Tape Automated Bonding) film, and a wiring substrate. The semiconductor chip 31 is electrically connected to the mounting substrate 51 via bumps 52. Specifically, an electrode pad (not shown) that the semiconductor chip 31 has on the circuit forming surface side and a terminal portion (not shown) that the mounting substrate 51 has are electrically connected via bumps 52. The bump 52 is, for example, a solder bump. Further, a thermosetting underfill agent 53 is interposed between the semiconductor chip 31 and the mounting substrate 51. For example, flip mounting of the semiconductor chip 31 on the mounting substrate 51 is realized by performing a so-called reflow process with the mounting substrate 51 accompanied by the semiconductor chip 31 with a film thereon.

  As described above, it is possible to manufacture a semiconductor device in which the film 10 ′ serving as a protective film is provided on the back surface of the semiconductor chip 31.

  The dicing tape-integrated adhesive sheet X can also be used as follows in the process of manufacturing a semiconductor device.

  In this semiconductor device manufacturing method, first, a modified region 30a is formed in the semiconductor wafer W as shown in FIGS. 7 (a) and 7 (b). The semiconductor wafer W has a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) are already formed on the first surface Wa side of the semiconductor wafer W, and wiring structures and the like (not shown) necessary for the semiconductor elements are already formed on the first surface Wa. Has been. The second surface Wb is a so-called back surface. In this step, after the wafer processing tape T2 having the adhesive surface T2a is bonded to the first surface Wa side of the semiconductor wafer W, the semiconductor wafer W is held on the wafer processing tape T2 and collected inside the wafer. A laser beam having a light spot is irradiated from the side opposite to the wafer processing tape T2 to the semiconductor wafer W along the planned dividing line, and the semiconductor wafer W enters the semiconductor wafer W due to ablation by multiphoton absorption. A modified region 30a is formed. The modified region 30a is a weakened region for separating the semiconductor wafer W into semiconductor chips. The method for forming the modified region 30a on the division line by laser light irradiation in the semiconductor wafer is described in detail in, for example, Japanese Patent Application Laid-Open No. 2002-192370. The laser light irradiation conditions in this embodiment are, for example, It adjusts suitably within the range of the following conditions.

[Laser irradiation conditions]
(A) Laser light Laser light source Semiconductor laser excitation Nd: YAG laser Wavelength 1064 nm
Laser light spot cross section 3.14 × 10 ^-8 cm ²
Oscillation form Q switch pulse Repetition frequency 100 kHz or less Pulse width 1 μs or less Output 1 mJ or less Laser light quality TEM00
Polarization characteristics Linearly polarized light (B) condenser lens Magnification 100 times or less NA 0.55
Transmittance with respect to laser light wavelength: 100% or less (C) Moving speed of the table on which the semiconductor substrate is placed 280 mm / second or less

  Next, in a state in which the semiconductor wafer W is held on the wafer processing tape T2, the semiconductor wafer W is thinned by grinding from the second surface Wb until reaching a predetermined thickness, whereby FIG. ), A semiconductor wafer 30A that can be separated into a plurality of semiconductor chips 31 is formed (wafer thinning step). In the semiconductor wafer 30A, the modified region 30a is exposed on the second surface Wb side.

  In this method, instead of the above-described method in which the wafer thinning process is performed after the process of forming the modified region 30a in the wafer W by laser irradiation, a grinding process for grinding the wafer W to a predetermined thickness is performed. Thereafter, a method of performing a step of forming the modified region 30a by laser irradiation in the thinned wafer W may be employed. Also by this method, it is possible to form a thin semiconductor wafer 30A that can be singulated into a plurality of semiconductor chips 31.

  Next, as shown in FIG. 8A, the semiconductor wafer 30A held on the wafer processing tape T2 is bonded to the film 10 of the dicing tape-integrated adhesive sheet X or the adhesive layer 12 thereof. . Thereafter, as shown in FIG. 8B, the wafer processing tape T2 is peeled off from the semiconductor wafer 30A.

  For example, after that, laser marking is performed by irradiating the laser mark layer 11 of the film 10 in the dicing tape-integrated adhesive sheet X from the substrate 21 side of the dicing tape 20 (laser marking step). By this laser marking, various pieces of information such as character information and graphic information are given to each semiconductor element that is later separated into semiconductor chips. In this step, it is possible to efficiently and efficiently perform laser marking on a large number of semiconductor elements in the semiconductor wafer 30A in one laser marking process.

Instead of the above-described radiation irradiation in the manufacturing process of the dicing tape-integrated adhesive sheet X, after the semiconductor wafer 30A is bonded to the film 10, ultraviolet light or the like is applied to the adhesive layer 22 from the substrate 21 side. Radiation may be irradiated. The irradiation amount is, for example, 50 to 500 mJ / cm ² . In the dicing tape-integrated adhesive sheet X, an area (irradiation area R shown in FIG. 1) where irradiation is performed as a measure for reducing the adhesive strength of the pressure-sensitive adhesive layer 22 is, for example, within the film 10 bonding area in the pressure-sensitive adhesive layer 22 This is an area excluding the peripheral edge.

  Next, after the ring frame 41 is pasted on the pressure-sensitive adhesive layer 22 in the dicing tape-integrated adhesive sheet X, the dicing tape-integrated adhesive property with the semiconductor wafer 30A as shown in FIG. 9A. The sheet X is fixed to the holder 42 of the expanding device.

  Next, a first expanding step (cleaving cool expanding step) under relatively low temperature conditions is performed as shown in FIG. 9B, and the semiconductor wafer 30A is divided into a plurality of semiconductor chips 31. The film 10 of the dicing tape-integrated adhesive sheet X is cleaved into small pieces of film 10 ′, and the semiconductor chip 31 with a film is obtained. In this step, the hollow cylindrical push-up member 45 provided in the expanding device is raised in contact with the dicing tape 20 on the lower side of the dicing tape-integrated adhesive sheet X in the drawing, and the dicing tape to which the semiconductor wafer 30A is bonded is attached. The dicing tape 20 of the integrated adhesive sheet X is expanded so as to be stretched in a two-dimensional direction including the radial direction and the circumferential direction of the semiconductor wafer 30A. This expansion is performed on the dicing tape 20 under conditions where a tensile stress of, for example, 1 to 100 MPa is generated. The temperature condition in this step is, for example, 0 ° C. or less, preferably −20 to −5 ° C., more preferably −15 to −5 ° C., and more preferably −15 ° C. The expanding speed (speed at which the push-up member 45 rises) in this step is, for example, 1 to 500 mm / second. Moreover, the amount of expansion (distance that the pushing-up member 45 rises) in this step is, for example, 50 to 400 mm. By such a cool expanding process, the film 10 of the dicing tape-integrated adhesive sheet X is cleaved into small pieces of the film 10 ′ to obtain the semiconductor chip 31 with a film. Specifically, in this step, cracks are formed in the fragile modified region 30a in the semiconductor wafer 30A, and the semiconductor chips 31 are separated. At the same time, in this step, in the film 10 in close contact with the adhesive layer 22 of the expanded dicing tape 20, deformation is suppressed in each region where the semiconductor chips 31 of the semiconductor wafer 30A are in close contact. The tensile stress generated in the dicing tape 20 acts on a portion of the wafer facing the crack forming portion in a state where such a deformation suppressing action does not occur. As a result, a portion of the film 10 that opposes the crack formation portion between the semiconductor chips 31 is cleaved. After this step, as shown in FIG. 9C, the push-up member 45 is lowered and the expanded state of the dicing tape 20 is released.

  Next, a second expanding step under relatively high temperature conditions is performed as shown in FIG. 10A, and the distance (separation distance) between the semiconductor chips 31 with a film is increased. In this step, the hollow cylindrical push-up member 45 provided in the expanding device is raised again, and the dicing tape 20 of the dicing tape-integrated adhesive sheet X is expanded. The temperature condition in the second expanding step is, for example, 10 ° C. or higher, and preferably 15 to 30 ° C. The expansion speed (speed at which the push-up member 45 rises) in the second expanding process is, for example, 0.1 to 10 mm / second. Moreover, the amount of expansion in the second expanding step is, for example, 3 to 16 mm. In this process, the separation distance of the semiconductor chip 31 with the film is widened so that the semiconductor chip 31 with the film can be appropriately picked up from the dicing tape 20 in the pickup process described later. After this step, as shown in FIG. 10B, the push-up member 45 is lowered and the expanded state of the dicing tape 20 is released. In order to prevent the separation distance of the semiconductor chip 31 with the film on the dicing tape 20 from being narrowed after the expanded state is released, the portion outside the holding region of the semiconductor chip 31 in the dicing tape 20 is heated before the expanded state is released. It is preferable to make it shrink.

Instead of the above-described radiation irradiation in the manufacturing process of the dicing tape-integrated adhesive sheet X or the above-described radiation irradiation after the semiconductor wafer 30A is bonded to the film 10, the above-described first expanding step or second expanding You may irradiate radiation, such as an ultraviolet-ray, with respect to the adhesive layer 22 from the base-material 21 side after a process. The irradiation amount is, for example, 50 to 500 mJ / cm ² . In the dicing tape-integrated adhesive sheet X, an area (irradiation area R shown in FIG. 1) where irradiation is performed as a measure for reducing the adhesive strength of the pressure-sensitive adhesive layer 22 is, for example, within the film 10 bonding area in the pressure-sensitive adhesive layer 22 This is an area excluding the peripheral edge.

  Next, the semiconductor chip 31 with a film is picked up from the dicing tape 20 after a cleaning process for cleaning the semiconductor chip 31 side of the dicing tape 20 with the semiconductor chip 31 with a film using a cleaning liquid such as water as necessary. A pick-up process is performed. Specifically, this is the same as described above with reference to FIG. The film-attached semiconductor chip 31 thus obtained is subjected to the mounting process described above with reference to FIG. As described above, a semiconductor device can be manufactured.

  As described above, the surface 12a of the adhesive layer-side surface 12a of the dicing tape-integrated adhesive sheet X is a peel test under conditions of 23 ° C., a peel angle of 180 °, and a pulling speed of 300 mm / min. In this case, the peel adhesive strength is 5 N / 10 mm or more, preferably 6 N / 10 mm or more, more preferably 7 N / 10 mm or more. The configuration in which the film 10 exhibits such a high peel adhesive strength with respect to the silicon wafer is suitable for realizing good holding of the work by the dicing tape-integrated adhesive sheet X or the film 10. The dicing tape-integrated adhesive sheet X having such a configuration does not necessarily require curing by heating to increase the adhesion to the workpiece of the film 10 after being bonded to the workpiece. It is suitable for avoiding or suppressing an excessive increase in the adhesion of the film 10 to the adhesive layer 22 of the tape 20. Therefore, such a dicing tape-integrated adhesive sheet X is suitable for realizing a good pickup of the semiconductor chip 31 with a film from the dicing tape 20 in the pickup process as described above.

  The surface 11a on the laser mark layer side of the film 10 of the dicing tape-integrated adhesive sheet X is, as described above, a peel test under the conditions of 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. In this case, the peel adhesive strength is 0.2 N / 10 mm or less, preferably 0.1 N / 10 mm or less, more preferably 0.07 N / 10 mm or less. Moreover, the peeling adhesive force (1st peeling adhesive force) in the peeling test on the conditions between 23 degreeC, the peeling angle of 180 degrees, and the tensile speed of 300 mm / min between the radiation-cured adhesive layer 22 and the film 10 is as follows. As described above, it is 0.15 N / 20 mm or less, preferably 0.13 N / 20 mm or less, more preferably 0.09 N / 20 mm or less. These configurations relating to the low peel adhesive strength are suitable for ensuring the peelability of the film 10 from the adhesive layer 22 of the dicing tape 20, and therefore the semiconductor chip 31 with a film from the dicing tape 20 in the pickup process as described above. Suitable for realizing a good pickup. In addition, these configurations relating to low peel adhesive strength increase, for example, the adhesion of the film 10 to the adhesive layer 22 of the dicing tape 20 over time during the storage period before use of the dicing tape integrated adhesive sheet X. Even if it is a case, it is suitable for avoiding excessive adhesion, and the radiation-cured pressure-sensitive adhesive layer 22 after storage of the dicing tape-integrated adhesive sheet X at 50 ° C. for 9 days About the difference between the peel adhesive force (second peel adhesive force) and the first peel adhesive force in the peel test between the film 10 and 23 ° C., peel angle 180 ° and tensile speed 300 mm / min. It contributes to restraining to 0.12 N / 20 mm or less, preferably 0.1 N / 20 mm or less, more preferably 0.07 N / 20 mm or less. That is, the said structure regarding low peeling adhesive force is suitable when ensuring storage stability regarding the adhesiveness between the adhesive layer 22 of the dicing tape 20, and the film 10 or its laser mark layer 11. FIG. Even in the case where the adhesion force of the film 10 to the adhesive layer 22 of the dicing tape 20 increases with time, it is possible to avoid the adhesion force from becoming excessive in the above-described pickup process. This contributes to realizing a good pickup of the semiconductor chip 31 with a film from 20.

  As described above, the dicing tape-integrated adhesive sheet X is suitable as a dicing tape-integrated back surface protective film for realizing a good pickup of the semiconductor chip 31 with a film from the dicing tape 20.

  As described above, the ratio of the thickness of the laser mark layer 11 to the thickness of the adhesive layer 12 in the film 10 is preferably 0.65 to 12, more preferably 0.75 to 7.5, and more preferably. Is between 0.85 and 5.5. Such a configuration is preferable in order to achieve both the characteristics required for the surface of the laser mark layer 11 in the film 10 and the characteristics required for the surface of the adhesive layer 12 that is the work pasting surface opposite to this. Specifically, for example, it is preferable to achieve both the above-described visibility of the marking information by laser marking in the laser mark layer 11 and the work adhesion of the surface on the adhesive layer side. In addition, when the dicing tape-integrated adhesive sheet X is used in the blade dicing process as described above, it may be formed on the wafer cut surface, that is, on the chip side surface due to impact or friction at the time of cutting with the dicing blade. From the viewpoint of suppressing a certain crack, the ratio value is preferably larger. On the other hand, when the dicing tape-integrated adhesive sheet X is used in the expanding process for cleaving as described above, from the viewpoint of realizing good cleaving property of the film 10, the value of the ratio is smaller. preferable.

  In the present embodiment, as described above, the dicing tape-integrated adhesive sheet X is stored at 23 ° C. and the peel angle between the pressure-sensitive adhesive layer 22 and the film 10 after being stored for 9 days at 50 ° C. The difference between the peel adhesive strength (second peel adhesive strength) and the first peel adhesive strength in the peel test under the conditions of 180 ° and a tensile speed of 300 mm / min is 0.12 N / 20 mm or less, preferably 0.1 N / 20 mm or less, more preferably 0.07 N / 20 mm or less. Such a configuration is suitable for realizing good storage stability in which an increase over time is suppressed with respect to the adhesion between the pressure-sensitive adhesive layer 22 of the dicing tape 20 and the film 10 or the laser mark layer 11 thereof.

[Example 1]
<Preparation of back surface protection film>
In the production of the back surface protective film in the dicing tape-integrated adhesive sheet, first, a first resin film that forms a laser mark layer (LM layer) and a second resin layer that forms an adhesive layer (AH layer). The resin film was produced separately.

In the production of the first resin film, first, acrylic resin A ₁ (trade name “Taisan Resin SG-P3”, weight average molecular weight 850,000, glass transition temperature Tg 12 ° C., manufactured by Nagase ChemteX Corporation) 100 mass Part, 52 parts by mass of epoxy resin B ₁ (trade name “KI-3000-4”, manufactured by Tohto Kasei Co., Ltd.) and 22 parts by mass of epoxy resin B ₂ (trade name “JER YL980”, manufactured by Mitsubishi Chemical Corporation) And 76 parts by mass of phenol resin C ₁ (trade name “MEH7851-SS”, manufactured by Meiwa Kasei Co., Ltd.) and filler (trade name “SO-25R”, silica, average particle size is 0.5 μm, Admatechs Co., Ltd.) 188 parts by mass, black dye (trade name “OIL BLACK BS”, manufactured by Orient Chemical Co., Ltd.), 25 parts by mass, and curing catalyst Z ₁ (trade name “CURESOL 2PZ”) ", Shikoku Kasei Kogyo Co., Ltd.) 22 parts by mass was added to methyl ethyl ketone and mixed to obtain a resin composition having a solid content concentration of 28% by mass. Next, the resin composition was applied on the silicone release treatment surface of a PET separator (thickness 50 μm) having a surface subjected to a silicone release treatment to form a resin composition layer. Next, the composition layer was heated at 130 ° C. for 2 minutes to be dried and thermally cured to produce a first resin film (film that will form a laser mark layer) having a thickness of 17 μm on the PET separator. .

In producing the second resin film, first, 100 parts by mass of acrylic resin A ₁ (trade name “Taisan Resin SG-P3”, manufactured by Nagase ChemteX Corporation) and epoxy resin B ₃ (trade name “EPPN-501HY”). , Nippon Kayaku Co., Ltd.) 66 parts by mass, phenol resin C ₂ (trade name “MEH7851-H”, Meiwa Kasei Co., Ltd.) 84 parts by mass, filler (trade name “SO-25R”, silica, average The particle size is 0.5 μm, manufactured by Admatechs Co., Ltd., 177 parts by mass and black dye (trade name “OIL BLACK BS”, manufactured by Orient Chemical Co., Ltd.) 15 parts by mass are added to methyl ethyl ketone and mixed. A resin composition having a solid content concentration of 28% by mass was obtained. Next, the resin composition was applied on the silicone release treatment surface of a PET separator (thickness 50 μm) having a surface subjected to a silicone release treatment to form a resin composition layer. Next, the composition layer is dried by heating at 130 ° C. for 2 minutes to produce an uncured second resin film (film that will form an adhesive layer) having a thickness of 8 μm on the PET separator. did.

  The 1st resin film on PET separator produced as mentioned above and the 2nd resin film on PET separator were pasted together using a laminator. Specifically, the exposed surfaces of the first and second resin films were bonded together under the conditions of a temperature of 100 ° C. and a pressure of 0.6 MPa. As described above, the back surface protective film of Example 1 was produced. The composition of the laser mark layer (LM layer) and the adhesive layer (AH layer) in each example and comparative example described later in Example 1 is listed in Tables 1 and 2 (in Tables 1 and 2, the composition of each layer is shown) The unit of each numerical value is a relative “part by mass” within the layer).

<Production of dicing tape>
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 100 parts by mass of 2-ethylhexyl acrylate, 19 parts by mass of 2-hydroxyethyl acrylate, and peroxidation as a polymerization initiator A mixture containing 0.4 part by mass of benzoyl and 80 parts by mass of toluene as a polymerization solvent was stirred at 60 ° C. for 10 hours in a nitrogen atmosphere (polymerization reaction). Thus, a polymer solution containing the acrylic polymer P ₁ was obtained. Next, a mixture containing the polymer solution containing the acrylic polymer P ₁ , 2-methacryloyloxyethyl isocyanate (MOI) and dibutyltin dilaurate as an addition reaction catalyst was heated at 50 ° C. for 60 hours in an air atmosphere. (Addition reaction). 0 in the reaction solution, the amount of the MOI is 12 parts by weight with respect to the acrylic polymer P ₁ 100 parts by weight, the amount of dibutyltin dilaurate, relative to the acrylic polymer P ₁ 100 parts by weight. 1 part by mass. By this addition reaction, a polymer solution containing an acrylic polymer P ₂ having a methacrylate group in the side chain was obtained. Next, 0.75 parts by mass of a polyisocyanate compound (trade name “Coronate L”, manufactured by Tosoh Corporation) and 2 parts by mass of photopolymerization are started with respect to 100 parts by mass of the acrylic polymer P _2. An agent (trade name “Irgacure 651”, manufactured by BASF) and toluene were added and mixed to obtain an adhesive composition having a solid content concentration of 28 mass%. Next, the pressure-sensitive adhesive composition layer was formed by applying the pressure-sensitive adhesive composition onto the silicone release-treated surface of the PET separator (thickness 50 μm) having the surface subjected to the silicone release treatment by using an applicator. . Next, the composition layer was heat-dried at 120 ° C. for 2 minutes to form an adhesive layer having a thickness of 5 μm on the PET separator. Next, using a laminator, a base material (trade name “NRW # 125”, thickness 125 μm, manufactured by Gunze Co., Ltd.) made of ethylene-vinyl acetate copolymer (EVA) is applied to the exposed surface of the adhesive layer. Bonded at room temperature. The bonded body was then stored at 23 ° C. for 72 hours. A dicing tape was produced as described above.

<Production of dicing tape integrated back protection film>
The above-mentioned back surface protective film of Example 1 with a PET separator was punched into a circle having a diameter of 330 mm. The above-mentioned dicing tape with a PET separator was punched into a circle having a diameter of 370 mm. And after peeling PET separator by the side of a laser mark layer from the said back surface protective film, after peeling PET separator from the said dicing tape, the laser mark layer side exposed in the back surface protective film, and the adhesive layer side exposed in the dicing tape Were laminated using a laminator. In this bonding, the bonding speed was 10 mm / min, the temperature condition was 23 ° C., and the pressure condition was 0.15 MPa. Further, the bonding was performed while aligning so that the center of the dicing tape and the center of the die bond film coincided. As described above, the dicing tape-integrated back surface protective film of Example 1 having a laminated structure including a dicing tape and a die bond film was produced.

[Example 2]
The thickness of the first resin film (resin film that will form a laser mark layer) is 23 μm instead of 17 μm and the second resin film (resin film that forms an adhesive layer) in the production of the back surface protective film A dicing tape-integrated back surface protective film of Example 2 was produced in the same manner as the dicing tape-integrated back surface protective film of Example 1 except that the thickness was changed to 2 μm instead of 8 μm.

Example 3
The thickness of the first resin film (resin film that will form the laser mark layer) in the production of the back surface protection film is 10 μm instead of 17 μm, and the second resin film (resin film that will form the adhesive layer) A dicing tape-integrated back surface protective film of Example 3 was produced in the same manner as the dicing tape-integrated back surface protective film of Example 1 except that the thickness was changed to 15 μm instead of 8 μm.

Example 4
In the production of the first resin film (resin film that will form a laser mark layer), acrylic resin A ₂ (trade name “Taisan Resin SG-70L”, weight average molecular weight is 90 instead of 100 parts by mass of acrylic resin A _1. The glass transition temperature Tg was −13 ° C., manufactured by Nagase ChemteX Corporation 100 parts by mass, and the content of the epoxy resin B ₁ (trade name “KI-3000-4”, manufactured by Toto Kasei Co., Ltd.) Was replaced by 52 parts by mass, and 43 parts by mass. The epoxy resin B ₂ (trade name “JER YL980”, manufactured by Mitsubishi Chemical Corporation) was replaced by 22 parts by mass and 18 parts by mass. The content of resin C ₁ (trade name “MEH7851-SS”, manufactured by Meiwa Kasei Co., Ltd.) was changed to 64 parts by mass instead of 76 parts by mass, filler (trade name “SO-25R”, The content of Admatex Co., Ltd.) was changed to 156 parts by mass instead of 188 parts by mass, and the content of black dye (trade name “OIL BLACK BS”, manufactured by Orient Chemical Industry Co., Ltd.) was 25 parts by mass. It was carried out except that the content of the curing catalyst Z ₁ (trade name “CURESOL 2PZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed to 18 parts by mass instead of 22 parts by mass. The dicing tape-integrated back surface protective film of Example 4 was produced in the same manner as the dicing tape-integrated back surface protective film of Example 1.

Example 5
In the production of the first resin film (resin film that will form a laser mark layer), acrylic resin A ₂ (trade name “Taisan Resin SG-70L”, weight average molecular weight is 90 instead of 100 parts by mass of acrylic resin A _1. The glass transition temperature Tg was −13 ° C., manufactured by Nagase ChemteX Corporation 100 parts by mass, and the content of the epoxy resin B ₁ (trade name “KI-3000-4”, manufactured by Toto Kasei Co., Ltd.) Was replaced by 52 parts by mass, and 43 parts by mass. The epoxy resin B ₂ (trade name “JER YL980”, manufactured by Mitsubishi Chemical Corporation) was replaced by 22 parts by mass and 18 parts by mass. The content of resin C ₁ (trade name “MEH7851-SS”, manufactured by Meiwa Kasei Co., Ltd.) was changed to 64 parts by mass instead of 76 parts by mass, filler (trade name “SO-25R”, The content of Admatex Co., Ltd.) was changed to 156 parts by mass instead of 188 parts by mass, and the content of black dye (trade name “OIL BLACK BS”, manufactured by Orient Chemical Industry Co., Ltd.) was 25 parts by mass. It was carried out except that the content was changed to 21 parts by mass and the content of the curing catalyst Z ₁ (trade name “CURESOL 2PZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed to 7 parts by mass instead of 22 parts by mass. A dicing tape-integrated back surface protective film of Example 5 was produced in the same manner as the dicing tape-integrated back surface protective film of Example 1.

Example 6
Similar to the dicing tape-integrated back surface protective film of Example 1 except that the thickness of the first resin film (resin film that will form the laser mark layer) is 7 μm instead of 17 μm in the production of the back surface protective film. Thus, a dicing tape-integrated back surface protective film of Example 6 was produced.

Example 7
The thickness of the first resin film (resin film that forms the laser mark layer) in the production of the back surface protection film is changed to 5 μm instead of 17 μm, and the second resin film (resin film that forms the adhesive layer) A dicing tape-integrated back surface protective film of Example 7 was produced in the same manner as the dicing tape-integrated back surface protective film of Example 1 except that the thickness was changed to 5 μm instead of 8 μm.

Example 8
The thickness of the first resin film (resin film that will form the laser mark layer) in the production of the back surface protective film is set to 8 μm instead of 17 μm, and the second resin film (resin film that forms the adhesive layer) A dicing tape-integrated back surface protective film of Example 8 was produced in the same manner as the dicing tape-integrated back surface protective film of Example 1 except that the thickness was changed to 17 μm instead of 8 μm.

[Comparative Example 1]
In the production of the back surface protective film, the content of the curing catalyst Z ₁ (trade name “CURESOL 2PZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) in the first resin film (resin film that will form a laser mark layer) is 22 parts by mass. A dicing tape-integrated back surface protective film of Comparative Example 1 was produced in the same manner as in the dicing tape-integrated back surface protective film of Example 1, except that the content was changed to 4 parts by mass.

[Comparative Example 2]
100 parts by mass of acrylic resin A ₁ (trade name “Taisan Resin SG-P3”, manufactured by Nagase ChemteX Corporation) and 9 parts by mass of epoxy resin B ₃ (trade name “EPPN-501HY”, manufactured by Nippon Kayaku Co., Ltd.) And 69 parts by mass of phenol resin C ₁ (trade name “MEH7851-SS”, manufactured by Meiwa Kasei Co., Ltd.) and 12 parts by mass of phenol resin C ₂ (trade name “MEH7851-H”, manufactured by Meiwa Kasei Co., Ltd.) In addition to 7 parts by mass of filler (trade name “SO-25R”, manufactured by Admatex Co., Ltd.) and methyl ethyl ketone, they were mixed to obtain a resin composition having a solid content concentration of 30% by mass. Next, the resin composition was applied on the silicone release treatment surface of a PET separator (thickness 50 μm) having a surface subjected to a silicone release treatment to form a resin composition layer. Next, the composition layer was dried by heating at 130 ° C. for 2 minutes to prepare a back protective film having a thickness of 25 μm on the PET separator. And the dicing tape of the comparative example 2 was carried out similarly to the dicing tape integrated back protective film of the example 1 except that the back surface protective film of the comparative example 2 was used instead of the above-described back surface protective film in the example 1. An integrated back protective film was produced.

[Comparative Example 3]
100 parts by mass of acrylic resin A ₂ (trade name “Taisan Resin SG-70L”, manufactured by Nagase ChemteX Corporation) and 52 parts by mass of epoxy resin B ₁ (trade name “KI-3000-4”, manufactured by Tohto Kasei Co., Ltd.) Part, epoxy resin B ₂ (trade name “JER YL980”, manufactured by Mitsubishi Chemical Corporation) 22 parts by mass, phenol resin C ₁ (trade name “MEH7851-SS”, manufactured by Meiwa Kasei Co., Ltd.) 76 parts by mass, 181 parts by mass of a filler (trade name “SO-25R”, manufactured by Admatechs Co., Ltd.), 15 parts by mass of a black dye (trade name “OIL BLACK BS”, manufactured by Orient Chemical Industry Co., Ltd.), and a curing catalyst Z ₂ ( 6 parts by mass of “Corazole 2PHZ-PW” (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is added to methyl ethyl ketone and mixed to obtain a resin composition having a solid content concentration of 30% by mass. It was. Next, the resin composition was applied on the silicone release treatment surface of a PET separator (thickness 50 μm) having a surface subjected to a silicone release treatment to form a resin composition layer. Next, the composition layer was dried by heating at 130 ° C. for 2 minutes to prepare a back protective film having a thickness of 25 μm on the PET separator. And the dicing tape of the comparative example 3 was carried out similarly to the dicing tape-integrated back protective film of the example 1 except that the back surface protective film of the comparative example 3 was used instead of the above-described back surface protective film in the example 1. An integrated back protective film was produced.

<Measurement of thickness>
The thickness of the laser mark layer (LM layer) and the adhesive layer (AH layer) in each of the dicing tape-integrated back surface protective films of Examples 1 to 8 and Comparative Example 1, and each dicing tape of Comparative Examples 2 and 3 The thickness of the back surface protective film in the body shape back surface protective film was measured as follows. First, the dicing tape integrated back surface protective film was frozen and then cut. Next, the section exposed by this cutting was observed using a microscope (trade name “Digital Microscope VHX-2000”, manufactured by Keyence Corporation), and the thickness of the layer to be measured was measured. Tables 1 and 2 list the maximum thickness (μm) of the layer to be measured.

<Peeling adhesive strength f ₁ of the back surface protective film>
Dicing tape side surface of the back surface protective film of the dicing tape-integrated backside protective film of Examples 1 to 8 and Comparative Examples 1 to 3, as follows, it was examined peel adhesion f ₁ with respect to the silicon wafer. First, in the dicing tape-integrated back surface protective film, the pressure-sensitive adhesive layer was cured by irradiating the pressure-sensitive adhesive layer with ultraviolet rays having an integrated irradiation light amount of 300 mJ / cm ² from the substrate side of the dicing tape. Next, a single-sided adhesive tape (trade name “BT-315”, manufactured by Nitto Denko Corporation) was bonded to the work adhesion side of the back surface protective film in the dicing tape-integrated back surface protective film. This bonding was performed by a pressure bonding operation in which a 2 kg hand roller was reciprocated once. Next, a laminate having a width of 10 mm and a length of 100 mm having a laminated structure of a dicing tape, a back surface protective film, and a single-sided adhesive tape was cut out from the bonded body. Next, the dicing tape was peeled from the laminate. Thereby, the test piece (width 10mm x length 100mm) which has the laminated structure of the back surface protective film and the single-sided adhesive tape which the dicing tape side surface exposes is obtained. Next, after confirming that the surface temperature of a silicon wafer (6 inches in diameter) placed on a hot plate with a set temperature of 80 ° C. is 75 ° C. or higher, the silicon wafer surface and the back surface protective film on the test piece The exposed surface was bonded together. This bonding was performed by a pressure bonding operation in which a 2 kg hand roller was reciprocated once. Then, after standing for 2 minutes on a hot plate, using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation), 23 ° C., peeling angle 180 ° and tensile speed 300 mm. A peel test was performed under the conditions of / min, and the peel adhesive force f ₁ (N / 10 mm) on the dicing tape side surface of the back surface protective film to the silicon wafer was measured. The results are listed in Tables 1 and 2. When peeling occurs at the interface between the above-mentioned single-sided adhesive tape (trade name “BT-315”) and the adhesive layer of the back surface protective film, it is shown in the table that the peeling adhesive force f ₁ is 8 N / 10 mm or more. Show.

<Peel Adhesion f ₂ of backside protective film>
For work attaching surface of the back surface protective film of the dicing tape-integrated backside protective film of Examples 1 to 8 and Comparative Examples 1 to 3, as follows, it was examined peel adhesion f ₂ to the silicon wafer. First, in the dicing tape-integrated back surface protective film, after the adhesive layer is cured by irradiating the adhesive layer with ultraviolet rays having an integrated irradiation light amount of 300 mJ / cm ² from the substrate side of the dicing tape, the dicing tape The back surface protective film was peeled off from the dicing tape of the body shape back surface protective film. Next, a single-sided adhesive tape (trade name “BT-315”, manufactured by Nitto Denko Corporation) was bonded to the dicing tape side surface of the peeled back surface protective film. Next, a test piece having a size of 10 mm in width and 100 mm in length having a laminated structure of a back surface protective film and a single-sided adhesive tape was cut out from the bonded body. Next, after confirming that the surface temperature of a silicon wafer (6 inches in diameter) placed on a hot plate with a set temperature of 80 ° C. is 75 ° C. or higher, the silicon wafer surface and the back surface protective film on the test piece Were pasted together. This bonding was performed by a pressure bonding operation in which a 2 kg hand roller was reciprocated once. Then, after standing for 2 minutes on a hot plate, using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation), 23 ° C., peeling angle 180 ° and tensile speed 300 mm. A peel test was performed under the conditions of / min, and the peel adhesive force f ₂ (N / 10 mm) of the work adhesion surface of the back surface protective film on the silicon wafer was measured. The results are listed in Tables 1 and 2. When peeling occurs at the interface between the above-mentioned single-sided adhesive tape (trade name “BT-315”) and the laser mark layer of the back surface protective film, it is shown in the table that the peeling adhesive force f ₂ is 8 N / 10 mm or more. Show.

<Peel adhesion between the adhesive layer and the backside protective film F _1>
About each dicing tape integrated type back surface protective film of Examples 1-8 and Comparative Examples 1-3, it is as follows and peeling adhesive force F1 (the _1st) between the radiation-cured adhesive layer and a back surface protective film 1 peel adhesive strength) was investigated. First, in the dicing tape-integrated back surface protective film, the pressure-sensitive adhesive layer was cured by irradiating the pressure-sensitive adhesive layer with radiation such as ultraviolet rays having an integrated irradiation light amount of 300 mJ / cm ² from the substrate side of the dicing tape. Next, a single-sided adhesive tape (trade name “BT-315”, manufactured by Nitto Denko Corporation) was bonded to the work bonding surface of the back surface protective film in the dicing tape-integrated back surface protective film. This bonding was performed by a pressure bonding operation in which a 2 kg hand roller was reciprocated once. Next, a test piece having a width of 100 mm and a length of 100 mm having a laminated structure of a back surface protective film and a single-sided adhesive tape was cut out from the bonded body. Then, using a tensile tester (trade name “Autograph AG-X”, manufactured by Shimadzu Corporation), the test piece was subjected to a peel test at 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. The peel adhesive force F ₁ (N / 20 mm) between the radiation-cured pressure-sensitive adhesive layer and the back surface protective film in the dicing tape-integrated back surface protective film was measured. The results are listed in Tables 1 and 2.

<Peel adhesion between the adhesive layer and the backside protective film F _2>
After each dicing tape-integrated back surface protective film of Examples 1-8 and Comparative Examples 1-3 was stored in an environment of 50 ° C. for 9 days, each of the dicing tape-integrated back surface protective films was subjected to radiation curing. The peel adhesive force F ₂ (first peel adhesive force) between the layer and the back surface protective film was examined. The test piece preparation method and the adhesive force measurement method / condition for examining the peel adhesive force F ₂ are the same as the test piece preparation method and the adhesive force measurement method / condition for examining the peel adhesive force F ₁ . The measured peel adhesion F ₂ (N / 20 mm) is listed in Tables 1 and 2.

<Laser marking evaluation>
About each dicing tape integrated back surface protection film of Examples 1-8 and Comparative Examples 1-3, laser marking property was investigated as follows. First, the silicon wafer was bonded together on the back surface protection film of the dicing tape integrated back surface protection film using a laminator. In this bonding, the temperature condition was 80 ° C., and the pressure condition was 0.15 MPa. Next, using a laser marking device (trade name “MD-S9910”, Keyence Co., Ltd.), the back protective film surface was irradiated with a laser through a dicing tape, and printing by laser marking was performed. In this laser marking, the laser power is 0.23 W, the marking speed is 300 mm / second, and the laser frequency is 10 kHz. Next, after the adhesive layer is cured by irradiating the adhesive layer from the substrate side of the dicing tape with an ultraviolet ray with an integrated irradiation light amount of 300 mJ / cm ² , the dicing tape is removed from the back surface protective film on the silicon wafer surface. It peeled. Next, with respect to the silicon wafer with the back surface protective film, a temperature profile (peak) conforming to PIC / JEDEC-J-STD-020 using a reflow apparatus (trade name “TAP30-407PM”, manufactured by Tamura Corporation). The reflow treatment was performed three times at a temperature of 260 ° C. Before and after the reflow treatment, a place for printing by laser marking using a microscope (trade name “Digital Microscope VHX-5600”, manufactured by Keyence Corporation) When the marking by laser marking is clearly visible, the laser marking property is evaluated as good (◯), and when the marking by laser marking is not clearly visible, the laser marking property is poor ( The results are shown in Tables 1 and 2.

<Storage stability evaluation>
In each of the dicing tape-integrated back protective films of Examples 1 to 8 and Comparative Examples 1 to 3, the storage stability was examined as follows. First, the dicing tape-integrated back surface protective film was stored in an environment of 50 ° C. for 9 days. Next, using a mounter (trade name “MA3000III”, manufactured by Nitto Seiki Co., Ltd.), the silicon wafer thinned by grinding on the back surface protective film of the dicing tape integrated back surface protective film (diameter 300 mm, thickness) 200 μm) was bonded together. In this bonding, the temperature condition was 75 ° C., the pressure condition was 0.15 MPa, and the bonding speed was 10 mm / second. Next, the silicon wafer on the dicing tape-integrated back surface protective film is formed into a 4 mm × 4 mm semiconductor chip by blade dicing using a dicer (trade name “DFD-6361”, manufactured by DISCO Corporation). Separated into pieces. In this blade dicing, first, a silicon wafer was cut to a half thickness with a Z1 blade, and then a dicing tape substrate was cut to a depth of 15 μm with a Z2 blade. Each semiconductor chip thus separated is accompanied by a small piece film derived from the back surface protective film of the dicing tape-integrated back surface protective film. Next, the pressure-sensitive adhesive layer was cured by irradiating the pressure-sensitive adhesive layer with ultraviolet rays having an integrated irradiation light amount of 300 mJ / cm ² from the substrate side of the dicing tape in the dicing tape-integrated back surface protective film. Next, the pick-up process for picking up a semiconductor chip with a film from a dicing tape was performed using a die bonder (trade name “SPA-300”, manufactured by Shinkawa Co., Ltd.). In this pick-up process, the expansion amount for extending the distance between the semiconductor chips is 5 mm, the pushing speed by the pushing member is 160 mm / second, the pushing amount by the pushing member is 200 μm, and the semiconductor chip is held by suction with the suction jig Was set to 100 milliseconds. And about storage stability, it is excellent (◎) when the number of semiconductor chips with a film that can be properly picked up after trying to pick up from 100 dicing tapes with respect to 100 semiconductor chips with a film is 90 or more. Evaluated as good (◯) when it is 70 or more and less than 90, evaluated as acceptable (Δ) when it was 50 or more and less than 70, and evaluated as impossible (x) when it was 50 or less. did. The results are listed in Tables 1 and 2.

[Evaluation]
The dicing tape-integrated back surface protective film of Examples 1 to 7 is suitable for realizing a good pickup of a semiconductor chip with a film in a pick-up process while including a back surface protective film having a good laser marking property.

X Dicing tape integrated adhesive sheet 10, 10 'film (adhesive sheet)
DESCRIPTION OF SYMBOLS 11 Laser mark layer 11a, 12a Surface 12 Adhesive layer 20 Dicing tape 21 Base material 22 Adhesive layer W, 30A Semiconductor wafer 30 Semiconductor wafer division body 30a Modification area 30b Dividing groove 31 Semiconductor chip 51 Mounting board 52 Bump

Claims (4)

A dicing tape having a laminated structure including a substrate and a radiation-curable pressure-sensitive adhesive layer;
An adhesive sheet having a laminated structure including a laser mark layer and an adhesive layer, and in close contact with the pressure-sensitive adhesive layer of the dicing tape on the laser mark layer side;
The surface on the adhesive layer side of the adhesive sheet exhibits a peel adhesive strength of 5 N / 10 mm or more in a peel test with respect to a silicon wafer at 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. ,
The surface of the adhesive sheet on the side of the laser mark layer has a peel adhesive strength of 0.2 N / 10 mm or less with respect to a silicon wafer in a peel test at 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. Indicate
The first peel adhesive strength in the peel test between the radiation-cured pressure-sensitive adhesive layer and the adhesive sheet under the conditions of 23 ° C., peel angle of 180 ° and tensile speed of 300 mm / min is 0.15 N / 20 mm. And
Second in a peel test between the pressure-sensitive adhesive layer cured by radiation after 9 days storage at 50 ° C. and the adhesive sheet at 23 ° C., a peel angle of 180 ° and a tensile speed of 300 mm / min. The dicing tape integrated adhesive sheet, wherein the difference between the peel adhesive strength and the first peel adhesive strength is 0.12 N / 20 mm or less.   The dicing tape-integrated adhesive sheet according to claim 1, wherein a value of a ratio of the thickness of the laser mark layer to the thickness of the adhesive layer is 0.65 to 12.   The dicing tape-integrated adhesive sheet according to claim 1, wherein the laser mark layer is a cured thermosetting layer.   The dicing tape-integrated adhesive sheet according to any one of claims 1 to 3, wherein the adhesive layer is a thermoplastic layer.

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