WO2021124724A1 - Adhesive tape for dicing and method for producing semiconductor chip - Google Patents

Adhesive tape for dicing and method for producing semiconductor chip Download PDF

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Publication number
WO2021124724A1
WO2021124724A1 PCT/JP2020/041705 JP2020041705W WO2021124724A1 WO 2021124724 A1 WO2021124724 A1 WO 2021124724A1 JP 2020041705 W JP2020041705 W JP 2020041705W WO 2021124724 A1 WO2021124724 A1 WO 2021124724A1
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WIPO (PCT)
Prior art keywords
silicone
mass
pressure
resin
sensitive adhesive
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PCT/JP2020/041705
Other languages
French (fr)
Japanese (ja)
Inventor
晃良 増田
敬之 下田
貴広 酒井
Original Assignee
マクセルホールディングス株式会社
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Application filed by マクセルホールディングス株式会社 filed Critical マクセルホールディングス株式会社
Priority to JP2021565362A priority Critical patent/JP7571049B2/en
Priority to KR1020227020562A priority patent/KR20220117234A/en
Priority to CN202080088643.XA priority patent/CN114868229A/en
Publication of WO2021124724A1 publication Critical patent/WO2021124724A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents

Definitions

  • the present invention relates to an adhesive tape for dicing used for dicing a semiconductor material used as a material for a semiconductor chip, and a method for manufacturing a semiconductor chip using the adhesive tape for dicing.
  • an adhesive tape for dicing used for manufacturing a semiconductor chip having an LED (Light Emitting Diode) or the like an adhesive tape having an adhesive layer made of an acrylic resin is known (see Patent Document 1). .. Further, as an adhesive tape for dicing used for producing a semiconductor chip having an LED or the like, an adhesive tape having an adhesive layer made of a silicone-based resin is known (see Patent Documents 2 and 3). Further, as a method of manufacturing a semiconductor chip using an adhesive tape for dicing, an adhesive tape is attached to the substrate side of a semiconductor element substrate in which a plurality of semiconductor elements are formed on the substrate, and the semiconductor element substrate is cut by a dicer. A method is known (see Patent Document 4).
  • Japanese Unexamined Patent Publication No. 2013-388408 Japanese Unexamined Patent Publication No. 2015-05216 Japanese Unexamined Patent Publication No. 2016-122812 Japanese Unexamined Patent Publication No. 2005-93503
  • an adhesive tape is attached to a semiconductor material in which a plurality of semiconductor elements are coated with a coating material such as a sealing resin or a phosphor, and dicing is performed.
  • a coating material such as a sealing resin or a phosphor
  • technologies corresponding to so-called wafer level CSP (chip scale package) processes have been proposed.
  • the adhesive tape is attached to the semiconductor material in which the semiconductor element is coated with the coating material, the adhesive strength is insufficient depending on the composition of the adhesive layer in the adhesive tape, the material of the coating material, etc.
  • the fragmented semiconductor chip may scatter.
  • the ball tack and adhesive strength of the adhesive layer are designed to be high in order to suppress the scattering of the semiconductor chip, when the obtained semiconductor chip is peeled from the adhesive tape, the adhesive remains attached to the semiconductor chip. So-called adhesive residue may occur.
  • the present invention has good adhesive force and tack force to a semiconductor material having a plurality of semiconductor elements coated with a coating material, and glue to the semiconductor chip when the semiconductor chip separated by dicing is peeled off. It is an object of the present invention to provide an adhesive tape for dicing in which the remainder is suppressed, and a method for manufacturing a semiconductor chip using the adhesive tape.
  • the present inventors have diligently studied the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape for dicing, and as a result, the pressure-sensitive adhesive layer is a silicone gum composed of at least (1) an organopolysiloxane containing a silicon atom-bonded alkenyl group.
  • the pressure-sensitive adhesive layer of the adhesive tape for dicing is thermally polymerized with a cross-linking agent on a silicone-based resin in which silicone gum and silicone resin are mixed in a predetermined ratio and have a predetermined amount of silicon atom-bonded alkenyl groups. It has been found that the following effects can be obtained by composing the pressure-sensitive adhesive composition to which the agent and the photosensitizing platinum (Pt) catalyst are added. First, when a semiconductor material having a plurality of semiconductor elements coated with a coating material is divided into a plurality of semiconductor chips, the pressure-sensitive adhesive layer is a heating / drying step for forming the pressure-sensitive adhesive layer on a substrate.
  • the adhesive layer Since a part of the silicone-based resin is cross-linked and cured (first-stage cross-linking reaction) by the thermal polymerization initiator, the adhesive layer is stable and has an appropriate cohesive force. It has been found that good tacking force and adhesive force suppress the scattering of the fragmented semiconductor chips during dicing.
  • the pressure-sensitive adhesive layer is irradiated with light such as ultraviolet rays, so that the light-sensitive platinum in the pressure-sensitive adhesive composition ( Pt)
  • the catalyst is activated, and the second-step cross-linking reaction (addition reaction) between the silicon atom-bonded alkenyl group of the silicone gum in the silicone-based resin and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent. Is promoted and the crosslink density is further increased, so that the cohesive force of the pressure-sensitive adhesive composition is further increased as compared with that before light irradiation.
  • the tack force of the pressure-sensitive adhesive layer is appropriately reduced, and the fracture mode in the holding force test is "interfacial peeling" or “does not fall” in the holding force test.
  • the pick-up property of the semiconductor chip from the adhesive tape for dicing is improved, and the adhesive residue on the semiconductor chip is suppressed.
  • the adhesive tape for dying of the present invention includes a base material and an adhesive layer laminated on the base material, and when a semiconductor material having a plurality of semiconductor elements coated with a coating material is divided into a plurality of semiconductor chips.
  • the pressure-sensitive adhesive layer is a silicone-based resin in which silicone gum (G) and silicone resin (R) are mixed, and is contained in one molecule as a cross-linking agent for the silicone-based resin.
  • the silicone-based resin comprises an organopolysiloxane having at least two or more silicon atom-bonded hydrogen atoms (SiH groups), a peroxide as a thermal polymerization initiator, and a light-sensitive platinum (Pt) catalyst.
  • the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) in the whole is in the range of 40.0 / 60.0 to 56.0 / 44.0 in terms of mass ratio.
  • the silicone gum (G) contains a silicone gum (G alk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group, and the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is 7. It is an adhesive tape for dying characterized in that it is in the range of 0 ⁇ 10 -7 mol / g or more and 5.5 ⁇ 10 -6 mol / g or less.
  • the pressure-sensitive adhesive layer is the silicon of the cross-linking agent contained in the pressure-sensitive adhesive composition with respect to the content (total amount) of the silicon atom-bonded alkenyl groups in the entire silicone-based resin contained in the pressure-sensitive adhesive composition. It can be characterized in that the molar ratio (SiH group / silicon atom-bonded alkenyl group) of the content (total amount) of the atomic-bonded hydrogen atom (SiH group) is in the range of 2.0 or more and 10.0 or less.
  • the content of the peroxide in the pressure-sensitive adhesive composition is 0.10 parts by mass or more and 3.00 parts by mass in terms of solid content with respect to 100 parts by mass of solid content of the entire silicone-based resin. It can be characterized by having a range of less than a part. Further, the pressure-sensitive adhesive layer can be characterized in that the peroxide is a diacyl peroxide. Further, in the pressure-sensitive adhesive layer, the content of the photosensitive platinum (Pt) catalyst in the pressure-sensitive adhesive composition is 0.10 parts by mass or more in terms of solid content with respect to 100 parts by mass of solid content of the entire silicone-based resin. It can be characterized in that it is in the range of 3.00 parts by mass or less.
  • the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 2.9 ⁇ 10 -6 mol / g or more and 4.1 ⁇ 10 -6 mol / g or less. It can be characterized by being. Further, it can be characterized in that all of the following conditions (a) to (c) are satisfied in the adhesive characteristics conforming to JIS Z 0237 (2009).
  • (A) The adhesive strength of the BA-SUS test plate before light irradiation is in the range of 2.8 N / 10 mm or more and 5.5 N / 10 mm or less.
  • the ball number values in the tilted ball tack test are the ball number value before light irradiation as BN0 and the ball number value after light irradiation. Is BN1, and the relationship is BN0> BN1.
  • C In the holding power test after light irradiation (temperature 40 ° C., relative humidity 33% RH, leaving time 2880 minutes), the fracture phenomenon at the time of dropping is the interface peeling between the adhesive layer and the BA-SUS test plate. There is, or it does not fall in the holding force test.
  • a plurality of the semiconductor elements in which the above-mentioned adhesive tape for dicing is sealed with a sealing resin made of a silicone resin are mounted on a substrate.
  • a method for manufacturing a semiconductor chip which includes an irradiation step of irradiating the dicing adhesive tape of the semiconductor element substrate with light, and a peeling step of peeling the dicing adhesive tape from the plurality of semiconductor chips.
  • a semiconductor material in which a plurality of semiconductor elements are coated with a coating material has good adhesive force and tack force before light irradiation, and is individualized by dicing after light irradiation. It is possible to provide an adhesive tape for dicing, which has good pick-up property of the semiconductor chip when the semiconductor chip is peeled off and suppresses adhesive residue on the semiconductor chip, and a method for manufacturing the semiconductor chip using the adhesive tape. it can.
  • FIG. 1 It is a figure which showed an example of the structure of the adhesive tape for dicing to which this embodiment is applied.
  • (A) to (e) are diagrams showing a method of manufacturing a semiconductor chip using the adhesive tape of the present embodiment. It is a schematic diagram which showed the relationship between the crosslink density of the silicone resin in the pressure-sensitive adhesive layer, and the result (drop time) of the holding force test of the pressure-sensitive adhesive tape 1.
  • FIG. 1 is a diagram showing an example of a configuration of a dicing adhesive tape 1 (hereinafter, simply referred to as an adhesive tape 1) to which the present embodiment is applied.
  • the adhesive tape 1 of the present embodiment is used for dicing a semiconductor material that is a source of a semiconductor chip in a process of manufacturing a semiconductor chip having a semiconductor element such as an LED (Light Emitting Diode) or a power semiconductor.
  • the adhesive tape 1 has a structure in which the pressure-sensitive adhesive layer 3 is laminated on the base material 2.
  • the adhesive tape 1 has an anchor coat layer between the base material 2 and the pressure-sensitive adhesive layer 3 to improve the adhesion between the base material 2 and the pressure-sensitive adhesive layer 3, if necessary. You may have it.
  • the surface of the base material 2 (the surface opposite to the surface facing the pressure-sensitive adhesive layer 3) may be surface-treated.
  • a release liner may be provided on the surface of the pressure-sensitive adhesive layer 3 (the surface opposite to the surface facing the base material 2).
  • the base material 2 of the present embodiment is made of a material that transmits light such as ultraviolet rays.
  • the material of the base material 2 is not particularly limited as long as it can transmit light such as ultraviolet rays, and for example, a plastic or the like that can transmit light such as ultraviolet rays can be used.
  • the fact that light such as ultraviolet rays can be transmitted does not mean that the transmittance of light such as ultraviolet rays is 100%, and at least the light-sensitive platinum (Pt) contained in the pressure-sensitive adhesive layer 3 will be described later. ) It is sufficient that the catalyst can transmit light to the extent that the addition reaction between the silicone resin and the cross-linking agent can be promoted.
  • the material of the base material 2 resin films such as polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, biaxially stretched polypropylene, aliphatic polyimide (transparent polyimide), polycycloolefin, fluororesin, and polyolefin resin are used. Can be used.
  • the base material 2 includes, for example, a composite film obtained by laminating polyethylene terephthalate and a polyolefin resin film, a composite film obtained by further laminating these composite films with a resin film, and a resin formed into a multi-layer by coextrusion. A film or the like may be used.
  • the base material 2 it is preferable to use a material containing polyethylene terephthalate as a main component.
  • the pressure-sensitive adhesive layer 3 of the present embodiment contains at least two or more silicon atom-bonded hydrogen atoms (SiH groups) in one molecule of a silicone-based resin in which silicone gum (G) and silicone resin (R) are mixed. It is composed of a pressure-sensitive adhesive composition containing a cross-linking agent for a silicone-based resin, a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst.
  • the silicone-based resin is defined as "a silicone gum (G ) containing a silicone gum (G alk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group” and "a silicone resin (R) made of an organopolysiloxane”. It consists of a mixed resin blended in the ratio of.
  • a silicone gum (G ) containing a silicone gum (G alk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group and "a silicone resin (R) made of an organopolysiloxane”. It consists of a mixed resin blended in the ratio of.
  • the silicone-based resin of the present embodiment includes "silicone gum (G) containing silicone gum (G alk ) made of organopolysiloxane containing a silicon atom-bonded alkenyl group” and "silicone resin (R) made of organopolysiloxane”. ) ”Is composed of a mixed resin blended so as to be in the range of 40.0 / 60.0 to 56.0 / 44.0. That is, the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) is in the range of 40.0 / 60.0 to 56.0 / 44.0 in terms of mass ratio. It consists of a mixed resin formulated as described above.
  • the silicone-based resin is configured such that the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 7.0 ⁇ 10 -7 mol / g or more and 5.5 ⁇ 10 -6 mol / g or less. It is more preferably configured so as to have a range of 2.9 ⁇ 10 -6 mol / g or more and 4.1 ⁇ 10 -5 mol / g or less.
  • mol / g means "amount of substance per 1 g of solid content of the entire silicone-based resin".
  • the silicon atom bond possessed by the silicone gum when the adhesive tape 1 is irradiated with light such as ultraviolet rays When the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is less than 7.0 ⁇ 10 -7 mol / g, the silicon atom bond possessed by the silicone gum when the adhesive tape 1 is irradiated with light such as ultraviolet rays.
  • the improvement of the cross-linking density by the second-stage cross-linking reaction (addition reaction) between the alkenyl group and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent becomes insufficient, the adhesive is hard to cure, and the cohesive force is increased. It becomes difficult to improve.
  • the desired reduction in tack force and the breaking mode in the holding force test cannot be obtained, and after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1. , There is a risk that the pickability of the individualized semiconductor chip will deteriorate, and there is a risk that adhesive residue will easily occur on the semiconductor chip or the like.
  • the silicone-based resin of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 contains silicone gum (G).
  • the silicone-based resin may be cured (first-step cross-linking reaction) by the thermal polymerization initiator before irradiation with light such as ultraviolet rays.
  • the pressure-sensitive adhesive layer 3 may become too hard due to excessive progress. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
  • the silicone-based resin of the present embodiment has "mixing ratio of silicone gum (G) and silicone resin (R) ((G) / (R))” and "content of silicon atom-bonded alkenyl group".
  • a silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group may be contained. That is, the silicone gum (G) may be a single substance of "silicone gum (G alk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group" or a mixture of two or more thereof, or "silicon".
  • sicone gum composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group (G alk ) and "silicone gum composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group (G 0)" contained in a silicone-based resin )
  • Silicone resin (R) composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group will be described in more detail.
  • the silicone gum (G alk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group is referred to as a silicone gum (G alk ) containing a silicon atom-bonded alkenyl group, or simply a silicone gum (G). It may be written as alk).
  • a silicone gum (G 0 ) composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group is referred to as a silicone gum (G 0 ) containing no silicon atom-bonded alkenyl group, or simply a silicone gum (G 0 ). May be done.
  • the silicone resin (R) composed of organopolysiloxane may be simply referred to as silicone resin (R).
  • the silicone gum (G alk ) composed of organopolysiloxane containing a silicon atom-bonded alkenyl group in the present embodiment is generally used as an addition reaction type silicone resin, that is, in one molecule on average. It is not particularly limited as long as it contains at least two silicon atom-bonded alkenyl groups. Specifically, as the silicone gum (G alk), those content of silicon-bonded alkenyl groups is in the range below 1.0 ⁇ 10 -6 mol / g or more 1.0 ⁇ 10 -1 mol / g Can be used.
  • the content of the silicon atom-bonded alkenyl group is 1.7 ⁇ 10 -6 mol from the viewpoint of controlling the adhesive properties of the pressure-sensitive adhesive layer 3 or making it easily available when a commercially available product is used. It is preferable to use one having a range of / g or more and 1.0 ⁇ 10 ⁇ 2 mol / g or less.
  • This silicone gum (G alk ) has an alkenyl group content of 7.0 ⁇ 10 -7 mol / g or more in the entire silicone-based resin in which the above-mentioned silicone gum (G) and silicone resin (R) are mixed 5
  • One type may be used alone or two or more types may be used in combination so as to have a range of .5 ⁇ 10 -6 mol / g or less.
  • the molecular structure of the organopolysiloxane containing the silicon atom-bonded alkenyl group constituting the silicone gum ( Galk ) is, for example, a linear structure in which the main chain portion is a repetition of diorganosiloxane units, and one of the molecular structures. Examples thereof include a structure containing a branched chain, a branched chain structure, and an annular structure. Of these, an organopolysiloxane having a linear structure is preferable from the viewpoint of mechanical strength and physical properties of the pressure-sensitive adhesive after irradiation with light such as ultraviolet rays.
  • the silicone gum (Galk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group may be in the form of oil or raw rubber, but is preferably in the form of raw rubber. If it is oily, viscosity of the silicone gum (G alk) consisting of organopolysiloxane at 25 ° C., or higher 1,000 mPa ⁇ s is preferable. If the viscosity is less than 1,000 mPa ⁇ s, the pressure-sensitive adhesive before and after irradiation with light such as ultraviolet rays may not exhibit the desired pressure-sensitive adhesive properties, or the adhesion between the pressure-sensitive adhesive layer 3 and the base material 2 may be inferior.
  • the viscosity of silicone gum ( Galk ) made of organopolysiloxane when dissolved in toluene so as to have a concentration of 30% by mass is preferably 100,000 mPa ⁇ s or less at 25 ° C. If the viscosity exceeds 100,000 mPa ⁇ s, it may be difficult to stir when preparing the pressure-sensitive adhesive composition.
  • the viscosity of the silicone gum ( Galk ) made of organopolysiloxane can be measured using a B-type rotational viscometer (using a BM type rotor, the same applies hereinafter).
  • silicone gum (Galk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group examples include those represented by the following general formula (1) or general formula (2), but are not limited thereto. Absent.
  • R 1 is a monovalent hydrocarbon group independently of each other and does not have an aliphatic unsaturated bond
  • X is an alkenyl group-containing organic group.
  • a is an integer of 0 to 3
  • m is an integer of 0 or more
  • n is an integer of 100 or more, where a and m do not become 0 at the same time, and m is 2 only when a is 0. It is the above integer.
  • m + n is a value at which the viscosity becomes 1,000 mPa ⁇ s or higher at 25 ° C. of the silicone gum (G alk) consisting of the organopolysiloxane.
  • R 1 a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms and having no aliphatic unsaturated bond is preferable.
  • examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl group such as cyclohexyl group; and aryl group such as phenyl group and tolyl group, and in particular, methyl group or phenyl group. Is preferable.
  • an alkenyl group-containing organic group having 2 to 10 carbon atoms is preferable.
  • a lower alkenyl group such as a vinyl group and an allyl group is preferable, and a vinyl group is particularly preferable from an industrial point of view.
  • the bonding position of the alkenyl group is not particularly limited, and may be a molecular chain end, a molecular chain side chain, or both a molecular chain end and a molecular chain side chain.
  • the appropriate range of the number of alkenyl groups varies depending on the content of the silicone resin (R) composed of organopolysiloxane contained in the silicone-based pressure-sensitive adhesive, the type and amount of the cross-linking agent, and the balance with other additive components. Although it cannot be said unconditionally, for example, it is preferably in the range of 0.1 or more and 3.0 or less with respect to 100 organogroups of the organopolysiloxane. Then, within this ratio range, the molecular weight may be adjusted so as to be within the above-mentioned viscosity range so that the number of the alkenyl groups in one molecule of organopolysiloxane is at least 2 on average. preferable.
  • the improvement of the cross-linking density by the second-step cross-linking reaction (addition reaction) between the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent for the alkenyl group and the silicone-based resin becomes insufficient, and the adhesive is difficult to cure. , It becomes difficult to improve the cohesive force.
  • the mixing ratio of the silicone gum (G) in the silicone-based resin of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 If the value is high, depending on the type and content of the thermal polymerization initiator, the curing of the silicone-based resin (first-step cross-linking reaction) may proceed too much due to the thermal polymerization initiator before irradiation with light such as ultraviolet rays. The pressure-sensitive adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
  • silicone gums containing such silicon-bonded alkenyl groups dimethylpolysiloxane with both molecular chain terminals blocked with dimethylvinylsiloxy groups at both molecular chain terminals with dimethylvinylsiloxy groups dimethylsiloxane-methylvinyl Siloxane copolymer, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain, dimethylvinylsiloxy group-blocked methylphenylpolysiloxane at both ends of the molecular chain, trimethylsiloxy group-blocked dimethylsiloxane / methyl at both ends of the molecular chain Vinylsiloxane copolymer, trimethylsiloxy group-blocking at both ends of the molecular chain dimethylsiloxane / methylvinylsiloxane / methylphenylsilox
  • the silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group in the present embodiment is generally used as a peroxide-curable silicone-based resin, that is, a silicon atom-bonded alkenyl group. It is not particularly limited as long as it does not contain.
  • the molecular structure of the organopolysiloxane constituting such a silicone gum (G 0 ) is, for example, a linear structure in which the main chain portion is a repetition of diorganosiloxane units, and a branched chain in a part of the molecular structure. Examples thereof include a structure containing a siloxane, a branched chain structure, or an annular structure.
  • the silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group may be in the form of oil or raw rubber, but is preferably in the form of raw rubber.
  • the viscosity of the silicone gum (G 0 ) made of organopolysiloxane is preferably 1,000 mPa ⁇ s or more at 25 ° C. If the viscosity is less than 1,000 mPa ⁇ s, the pressure-sensitive adhesive before and after irradiation with light such as ultraviolet rays may not exhibit the desired pressure-sensitive adhesive properties, or the adhesion between the pressure-sensitive adhesive layer 3 and the base material 2 may be inferior.
  • the viscosity of silicone gum (G 0 ) made of organopolysiloxane when dissolved in toluene so as to have a concentration of 30% by mass is preferably 100,000 mPa ⁇ s or less at 25 ° C. If the viscosity exceeds 100,000 mPa ⁇ s, it may be difficult to stir when preparing the pressure-sensitive adhesive composition.
  • the viscosity of the silicone gum (G 0 ) made of organopolysiloxane can be measured using a B-type rotational viscometer.
  • silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group examples include those represented by the following general formula (3) or general formula (4), but are not limited thereto. Absent.
  • R 4 is a monovalent hydrocarbon group which is independent of each other and does not have an aliphatic unsaturated bond, and t is an integer of 100 or more.
  • the viscosity of the silicone gum (G 0 ) made of the above diorganopolysiloxane at 25 ° C. is a value of 1,000 mPa ⁇ s or more.
  • R 4 a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms and having no aliphatic unsaturated bond is preferable.
  • examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl group such as cyclohexyl group; and aryl group such as phenyl group and tolyl group, and methyl group is particularly preferable.
  • the silicone resin (R) composed of the organopolysiloxane in the present embodiment is an organopolysiloxane having R 2 3 SiO 0.5 unit (M unit) and SiO 2 unit (Q unit), and is generally a silicone-based pressure-sensitive adhesive. It is a so-called MQ resin used in the above.
  • the silicone resin (R) composed of this organopolysiloxane basically does not have an alkenyl group in the molecule, and conventionally known ones can be used.
  • R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include those exemplified as R 1 described above.
  • the organopolysiloxane constituting the silicone resin (R) has R 2 3 SiO 0.5 units and SiO 2 units in the range of 0.5 or more and 1.7 or less in a molar ratio of R 2 3 SiO 0.5 units / SiO 2 units. It is preferable to contain it so as to become. If the molar ratio of R 2 3 SiO 0.5 unit / SiO 2 unit is less than 0.5, the adhesive strength and tack strength of the obtained pressure-sensitive adhesive layer 3 may decrease. On the other hand, if the molar ratio of R 2 3 SiO 0.5 unit / SiO 2 unit exceeds 1.7, the adhesive strength and holding power of the obtained pressure-sensitive adhesive layer 3 may decrease.
  • the organopolysiloxane constituting the silicone resin (R) may have an OH group.
  • the content of the OH group is preferably 4.0% by mass or less with respect to the total mass of the organopolysiloxane. If the content of OH groups exceeds 4.0% by mass, the curability of the pressure-sensitive adhesive may decrease.
  • organopolysiloxane Two or more kinds of the above-mentioned organopolysiloxane may be used in combination. Further, the organopolysiloxane may have R 2 SiO 1.5 units (T units) and / or R 2 2 SiO units (D units) as long as the characteristics of the present invention are not impaired.
  • Silicone gum (G alk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group
  • Silicone gum (G 0 ) composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group
  • Consists of an organopolysiloxane The “silicone resin (R)” may usually be simply mixed and used.
  • a silicone gum ( Galk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group a case where the organopolysiloxane represented by the above general formula (2) is contained, or an organo without a silicon atom-bonded alkenyl group is contained.
  • the silicone gum (G 0 ) composed of polysiloxane contains the organopolysiloxane represented by the above general formula (4)
  • the silicone gum (G alk ) and silicone are provided as long as the characteristics of the present invention are not impaired.
  • the resin (R) or the silicone gum (G 0 ) and the silicone resin (R) may be reacted in advance to be used as a (partial) condensation reaction product.
  • the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) in the entire silicone-based resin contained in the pressure-sensitive adhesive layer 3 of the present embodiment is 40.0 / by mass ratio. It is in the range of 60.0 to 56.0 / 44.0.
  • the total amount of each silicone gum (G) is regarded as the mass of the silicone gum (G) in the entire silicone-based resin.
  • silicone gum (G alk ) and silicone gum (G 0 ) are used in combination as the silicone gum (G)
  • the mass of the silicone gum (G) in the entire silicone-based resin is the mass of the silicone gum (G alk ). It is the total amount with the mass of silicone gum (G 0).
  • the total amount of each silicone resin is regarded as the mass of the silicone resin (R) in the entire silicone resin.
  • the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) is less than the lower limit of the above range.
  • the silicon atom-bonded alkenyl group of the silicone gum (G) and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent for the silicone-based resin when the adhesive tape 1 is irradiated with light such as ultraviolet rays when the adhesive tape 1 is irradiated with light such as ultraviolet rays.
  • the contribution of the improvement of the cross-linking density by the second-stage cross-linking reaction (addition reaction) becomes insufficient, the adhesive is hard to cure, and the cohesive force is hard to improve.
  • the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) has an upper limit value in the above range. If it exceeds the limit, the curing of the silicone-based resin (first-stage cross-linking reaction) may proceed too much due to the thermal polymerization initiator before irradiation with light such as ultraviolet rays, and the pressure-sensitive adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
  • the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) was set to 40.
  • the range from 0 / 60.0 to 56.0 / 44.0 the following effects can be realized. That is, in the stage before irradiation with light such as ultraviolet rays, the pressure-sensitive adhesive layer 3 is in a state in which a part of the silicone-based resin is crosslinked / cured (first-stage crosslinking reaction) by the thermal polymerization initiator.
  • the silicone-based resin of the pressure-sensitive adhesive layer 3 has a silicon atom-bonded alkenyl group content of 7.0 ⁇ 10 -7 mol / g or more in the entire silicone-based resin as described above.
  • the silicon atom-bonded alkenyl group of the silicone gum (G) and the silicon atom-bonded hydrogen atom of the cross-linking agent for the silicone-based resin proceeds sufficiently.
  • the curing of the pressure-sensitive adhesive layer 3 further progresses, so that the crosslink density is increased and the cohesive force is further improved, so that a desired decrease in tack force and a fracture mode in the holding force test can be obtained.
  • the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is preferably in the range of 2.9 ⁇ 10 -6 mol / g or more and 4.1 ⁇ 10 -6 mol / g or less.
  • the pressure-sensitive adhesive tape 1 having more stable dicing characteristics can be realized.
  • silicone-based resin in which the silicone gum (G) and the silicone resin (R) of the present invention are mixed those prepared by appropriately combining commercially available materials exemplified below can also be used.
  • a mixture prepared by appropriately combining means "the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin of the pressure-sensitive adhesive layer 3 is 7.0 ⁇ 10 -7 mol / g or more 5.5 ⁇ .
  • the mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) is 40.0 / 60.0 to 56.0 / 44.0. It means "a product prepared by appropriately combining and mixing individual materials so as to fall within the range of.” Examples of individual commercially available materials for mixing and preparing in appropriate combinations include the following materials (1) to (4).
  • silicone-based resin containing a silicon atom-bonded alkenyl group examples include (1) a commercially available addition-reaction silicone-based pressure-sensitive adhesive in which silicone gum (Galk ) and silicone resin (R) are mixed in a predetermined ratio, and (2). ) An addition-reaction type silicone-based mold release agent containing silicone gum (G alk) as a main component can be mentioned. Further, as the silicone-based resin containing no silicon atom-bonded alkenyl group, (3) a commercially available peroxide-curable silicone-based adhesive in which silicone gum (G 0 ) and silicone resin (R) are mixed in a predetermined ratio. Examples thereof include agents and (4) a single product of a commercially available silicone resin (R).
  • the silicone-based resin containing the silicon atom-bonded alkenyl group includes (1) a commercially available addition-reaction silicone-based adhesive in which silicone gum (Galk ) and silicone resin (R) are mixed in a predetermined ratio.
  • Agents (2) commercially available addition-reaction type silicone-based mold release agents containing silicone gum (G alk) as a main component, and the like can be used.
  • specific commercially available materials will be illustrated.
  • the commercially available addition reaction silicone adhesive is not particularly limited as long as it is generally used as a silicone adhesive for silicone adhesive tapes.
  • a type in which a cross-linking agent is added can also be used, but if the content of the silicon atom-bonded hydrogen atom (SiH group) contained in the cross-linked agent is unknown, the content is determined by the content. It can be obtained by analysis of 1 H-NMR (nuclear magnetic resonance) spectrum measurement described later.
  • the commercially available addition-reaction type silicone-based mold release agent is as long as it is generally used as a release treatment agent for a silicone-based mold release film for adhesive tapes.
  • either a type without a cross-linking agent or a type with a cross-linking agent may be used, and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linked agent contained therein may be used.
  • the content can be determined by analysis of 1 H-NMR (nuclear magnetic resonance) spectrum measurement or the like.
  • silicone-based resin that does not contain a silicon atom-bonded alkenyl group
  • examples of the silicone-based resin that does not contain a silicon atom-bonded alkenyl group include a commercially available peroxide-curable silicone-based pressure-sensitive adhesive in which silicone gum (G 0) and silicone resin (R) are mixed in a predetermined ratio.
  • a commercially available silicone resin (R) alone can be used.
  • specific commercially available materials will be illustrated.
  • peroxide Curable Silicone Adhesive The above-mentioned commercially available peroxide curable silicone adhesive is particularly limited as long as it is generally used as a silicone adhesive for silicone adhesive tapes. Not done. Specifically, for example, KR-100, KR-101-10 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., YR3340, YR3286, PSA610-SM, XR37-B6722 manufactured by Momentive Performance Materials Co., Ltd. , YF3897 (all trade names), SH4280, SH4282, SE4200, BY24-717, BY24-715, Q2-7735 (all trade names) manufactured by Dow Toray Co., Ltd. and the like.
  • Silicone Resin As a single product of the commercially available silicone resin (R), specifically, for example, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XC96-723, manufactured by Momentive Performance Materials Co., Ltd. 2D SILANOL FLUID (both are trade names) and the like can be mentioned.
  • these commercially available silicone-based resins have a silicon atom-bonded alkenyl group content of 7.0 ⁇ 10 -7 mol / g or more in the entire silicone-based resin of the pressure-sensitive adhesive layer 3 of 5.5 ⁇ 10 -6.
  • the mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) is in the range of 40.0 / 60.0 to 56.0 / 44.0. It may be used in a state of being mixed and prepared by appropriately combining them so as to be.
  • silicone-based resins include (a) a silicone-based resin obtained by adding an addition-reaction type silicone-based release agent to an addition-reaction type silicone-based pressure-sensitive adhesive. (B) A silicone-based resin to which a peroxide-curable silicone-based pressure-sensitive adhesive and / or a silicone resin (R) is further added may be used as the main component of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3.
  • "as the main component” means that the pressure-sensitive adhesive composition occupies 75 parts by mass or more when the solid content is 100 parts by mass, and preferably 90 parts by mass. The above is more preferably 95 parts by mass or more.
  • the cross-linking agent in the present embodiment exhibits a function as a cross-linking agent for the silicone-based pressure-sensitive adhesive by irradiating the pressure-sensitive adhesive layer 3 with light such as ultraviolet rays. That is, the cross-linking agent in the present embodiment is a silicone-based resin when the light-sensitive platinum (Pt) catalyst in the silicone-based pressure-sensitive adhesive is activated by irradiating the pressure-sensitive adhesive layer 3 with light such as ultraviolet rays. by addition reaction against silicon-bonded alkenyl groups silicone gum (G alk) have contained, used to crosslink the pressure-sensitive adhesive layer 3.
  • Pt light-sensitive platinum
  • G alk silicon-bonded alkenyl groups silicone gum
  • an organopolysiloxane (organohydrogenpolysiloxane) having at least two, preferably three or more silicon atom-bonded hydrogen atoms (SiH groups) in one molecule is used.
  • an organopolysiloxane having a silicon atom-bonded hydrogen atom (SiH group) may be simply referred to as an organohydrogenpolysiloxane.
  • Examples of the molecular structure of the organohydrogenpolysiloxane used as a cross-linking agent include linear, linear with partial branches, branched chain, and network.
  • the organohydrogenpolysiloxane preferably has a viscosity at 25 ° C. of 1 mPa ⁇ s or more and 5,000 mPa ⁇ s or less. The viscosity can be measured using a B-type rotational viscometer.
  • organohydrogenpolysiloxane used as a cross-linking agent conventionally known ones can be used.
  • examples of this organohydrogenpolysiloxane include those represented by the following general formula (5) or general formula (6), but are not limited thereto.
  • R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • b is 0 or 1
  • p and q are integers. This is a value at which the viscosity of the organohydrogenpolysiloxane at 25 ° C. is 1 mPa ⁇ s or more and 5,000 mPa ⁇ s or less.
  • r is an integer of 2 or more
  • s is an integer of 0 or more
  • the organohydrogenpolysiloxane may be a mixture of two or more.
  • R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms.
  • alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl group such as cyclohexyl group; and aryl group such as phenyl group and trill group, and alkenyl group such as vinyl group and allyl group can be mentioned.
  • a methyl group or a phenyl group is preferable.
  • the content of the organohydrogenpolysiloxane used as the cross-linking agent in the pressure-sensitive adhesive layer 3 of the present embodiment is the content of the silicon atom-bonded alkenyl group of the silicone gum (Galk ) and the silicon contained in the organohydrogenpolysiloxane. Since the appropriate range changes depending on the content of the atomic-bonded hydrogen atom, it cannot be said unconditionally, but usually, for example, the silicon atom of the silicone-based resin contained in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 is used.
  • the molar ratio of the content (total amount) of the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent contained in the pressure-sensitive adhesive composition to the content (total amount) of the bonded alkenyl group is in the range of 2.0 or more and 10.0 or less. Is preferable.
  • the content of organohydrogenpolysiloxane is less than the above lower limit
  • the adhesive tape 1 is irradiated with light such as ultraviolet rays
  • the silicon atom-bonded alkenyl group of the silicone gum and the silicon atom-bonded hydrogen atom of the cross-linking agent are present.
  • the improvement of the cross-linking density by the second-stage cross-linking reaction (addition reaction) with the (SiH group) becomes insufficient, the adhesive is hard to cure, and the cohesive force is hard to be improved.
  • organohydrogenpolysiloxane if the content of organohydrogenpolysiloxane exceeds the above upper limit, unreacted organohydrogenpolysiloxane may contaminate the semiconductor chip. Further, the silicon atom-bonded hydrogen atom (SiH group) in the unreacted organohydrogenpolysiloxane reacts with oxygen and water in the air to change to SiOH, and the adhesive force of the pressure-sensitive adhesive layer 3 to the adherend is large. As a result, the pickability of the individualized semiconductor chip may deteriorate.
  • SiH group silicon atom-bonded hydrogen atom
  • the content of the cross-linking agent in the pressure-sensitive adhesive layer 3 of the present embodiment is the silicon of the entire cross-linking agent with respect to the content (total amount) of the silicon atom-bonded alkenyl groups in the entire silicone-based resin in the pressure-sensitive adhesive layer 3.
  • the molar ratio of the content (total amount) of the atomically bonded hydrogen atom (SiH group) may be adjusted to be within the above range.
  • the content of the cross-linking agent satisfying this range varies depending on the number of silicon atom-bonded hydrogen atoms (SiH groups) contained in the cross-linking agent, but for example, the silicone type contained in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3.
  • the cross-linking agent may be added so that the solid content is in the range of 0.20 parts by mass or more and 20.00 parts by mass or less with respect to 100 parts by mass of the solid content of the entire resin.
  • the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays when the semiconductor chip is peeled off from the adhesive tape for dying. Then, the photosensitive platinum (Pt) catalyst in the silicone-based pressure-sensitive adhesive is activated, and the silicon atom-bonded alkenyl group contained in the silicone gum (Galk) in the silicone-based resin and the silicon atom contained in the cross-linking agent for the silicone-based resin.
  • Pt photosensitive platinum
  • the second-stage cross-linking reaction (addition reaction) with the bonded hydrogen atom (SiH group) is promoted, the cross-linking density becomes high, and the cohesive force of the adhesive becomes larger than that before light irradiation such as ultraviolet rays. ..
  • the tacking force of the pressure-sensitive adhesive layer 3 is appropriately reduced, good pick-up performance when peeling the semiconductor chip or the like from the pressure-sensitive adhesive tape 1 can be realized, and adhesive residue on the semiconductor chip or the like can be suppressed.
  • the cross-linking agent is generally used as a cross-linking agent for an addition-reaction type silicone-based pressure-sensitive adhesive, that is, an organopolysiloxane (organo) having at least two silicon atom-bonded hydrogen atoms (SiH groups) in one molecule. It may be (hydrogen polysiloxane), and is not particularly limited. Specific examples thereof include X-92-122 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. and BY24-741 (trade name) manufactured by Dow Toray Co., Ltd. If the content of the silicon atom-bonded hydrogen atom (SiH group) contained in these cross-linking agents is unknown, the content can be determined by analysis of 1 H-NMR (nuclear magnetic resonance) spectrum measurement described later. it can.
  • organopolysiloxane organo having at least two silicon atom-bonded hydrogen atoms (SiH groups) in one molecule. It may be (hydrogen polysiloxane), and is not particularly limited
  • the photosensitive platinum (Pt) catalyst is used to accelerate curing by an addition reaction (hydrosilylation) between the silicone resin constituting the pressure-sensitive adhesive layer 3 and a cross-linking agent by irradiation with light such as ultraviolet rays.
  • the wavelength of light that can be used to promote curing by the addition reaction between the silicon atom-bonded alkenyl group of the silicone gum (Galk ) in the silicone-based pressure-sensitive adhesive and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent is , 240 nm or more and preferably 400 nm or less.
  • the photosensitive platinum (Pt) catalyst it is preferable to use a photoactive cyclopentadienyl platinum (IV) compound from the viewpoint of good photosensitivity and reaction rate.
  • the photoactive cyclopentadienyl platinum (IV) compound is not particularly limited, but for example, (cyclopentadienyl) dimethyltrimethylsilylmethyl platinum, (cyclopentadienyl) diethyltrimethylsilylmethyl platinum, (cyclo).
  • the cyclopentadienyl ring in the above-mentioned compounds includes methyl, chloro, fluoro, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, phenyl, fluorophenyl, chlorophenyl, methoxy, naphthyl, biphenyl, anthracenyl, and the like.
  • the cyclopentadienyl ring in the above-mentioned compound includes one that is not substituted, one that is substituted with one or more aromatic organic groups, one that is substituted with one or more aliphatic organic groups, and one or more. Those substituted with an aromatic organic group and one or more aliphatic organic groups are preferable. Further, as the organic group substituted with the cyclopentadienyl ring, naphthyl, biphenyl, anthracenyl, phenanthryl and pyrenyl are preferable.
  • the content of the photosensitive platinum (Pt) catalyst in the pressure-sensitive adhesive layer 3 of the present embodiment is the same as that of the silicon atom-bonded alkenyl group contained in the silicone gum (Galk) in the silicone-based pressure-sensitive adhesive by irradiation with light such as ultraviolet rays.
  • the cross-linking agent is not particularly limited as long as it can promote the addition reaction with the silicon atom-bonded hydrogen atom (SiH group).
  • the content of the photosensitive platinum (Pt) catalyst in the pressure-sensitive adhesive layer 3 of the present embodiment is, for example, relative to 100 parts by mass of the solid content of the entire silicone-based resin in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3.
  • the solid content is preferably in the range of 0.10 parts by mass or more and 3.00 parts by mass or less, and more preferably in the range of 0.20 parts by mass to 1.00 parts by mass.
  • the content of the photosensitive platinum (Pt) catalyst is less than 0.10 parts by mass, the silicon atom-bonded alkenyl group contained in the silicone gum and the silicon contained in the cross-linking agent when the adhesive tape 1 is irradiated with light such as ultraviolet rays.
  • the cross-linking reaction (addition reaction) with the atomic-bonded hydrogen atom (SiH group) does not proceed sufficiently, the improvement of the cross-linking density becomes insufficient, the adhesive is hard to cure, and the cohesive force is hard to be improved.
  • the desired reduction in tack force and the breaking mode in the holding force test cannot be obtained, and after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1. , There is a risk that the pickability of the individualized semiconductor chip will deteriorate, and there is a risk that adhesive residue will easily occur on the semiconductor chip or the like.
  • the content of the photosensitive platinum (Pt) catalyst exceeds 3.00 parts by mass, the above-mentioned cross-linking reaction (addition reaction) proceeds sufficiently. Therefore, for example, even if the content is 10.0 parts by mass, the adhesive tape 1 There is no particular problem with the characteristics of the above, but it is not preferable from the viewpoint of economic efficiency.
  • thermal polymerization initiator As the thermal polymerization initiator in this embodiment, a peroxide, more specifically, an organic peroxide is used.
  • the thermal polymerization initiator in the present embodiment is suitable so that the semiconductor chip or the like, which is a cut piece, does not scatter with respect to the adhesive layer 3 of the adhesive tape 1 before being irradiated with light such as ultraviolet rays. It is used to impart adhesive strength and tack strength. That is, the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 generates radicals due to the heat applied in the heating / drying step when forming the pressure-sensitive adhesive layer 3.
  • the radical mainly attacks a part of the methyl group and the alkenyl group of the silicone gum (G) in the silicone resin to form a methylene chain, and appropriately crosslinks and cures the pressure-sensitive adhesive layer 3.
  • the methyl group and the alkenyl group first react with each other, and at the same time or subsequently, the cross-linking reaction proceeds between the methyl groups or between the cross-linked portion and the methyl group. Be done.
  • an appropriate cohesive force is imparted to the pressure-sensitive adhesive layer 3, and as a result, an appropriate adhesive force and tack force that do not cause scattering of semiconductor chips or the like that are cut pieces during dicing can be stably realized. it can.
  • the peroxide used as the thermal polymerization initiator is not particularly limited as long as it decomposes to generate free oxygen radicals, but for example, dibenzoyl peroxide and 4,4'-dimethyldibenzoyl.
  • Diacyl peroxides having a 1-minute half-life temperature of 85 ° C or higher and 135 ° C or lower, such as oxides and diisonanoyl peroxides; dicumyl peroxide, t-butyl-cumyl peroxide, 2,5-dimethyl-2,5- Di (t-butylperoxy) hexane, 1,1'-di-t-butylper
  • dialkyl peroxides having a 1-minute half-life temperature of 170 ° C. to 200 ° C.
  • Commercially available products include, for example, diacyl peroxides such as NOF BMT-K40 and Nyper BW (both trade names) manufactured by NOF CORPORATION, and dialkyl peroxides such as Perbutyl C manufactured by NOF CORPORATION and Park Mill. Examples thereof include D and perbutyl P (both are trade names).
  • the above peroxide is 1 from the viewpoint of ensuring the deformation temperature (heat resistance) of the base material 2 of the adhesive tape 1 and the residual amount of alkenyl groups of the silicone gum (Galk) in the state before light irradiation such as ultraviolet rays. It is preferable to use diacyl peroxides having a half-life temperature of about 85 ° C. to 135 ° C. per minute. That is, when diacyl peroxides are used as the peroxide, the pressure-sensitive adhesive layer 3 is formed as compared with the case where dialkyl peroxides (with a half-life temperature of about 170 ° C. to 200 ° C. for 1 minute) are used.
  • the base material 2 of the adhesive tape 1 can be decomposed even at a low heating temperature and a short drying time, which are less likely to be thermally deformed.
  • the reaction between the methyl groups of the silicone gum (G) is more likely to proceed preferentially than the reaction between the methyl group and the alkenyl group of the silicone gum (G), and the cross-linking agent has when irradiated with light such as ultraviolet rays.
  • the content of the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 differs depending on the heating temperature / time, the decomposition temperature of the organic peroxide used (1 minute half-life temperature), the mixing ratio of the silicone gum (G), and the like.
  • the solid content may be in the range of 0.10 parts by mass or more and 3.00 parts by mass or less with respect to 100 parts by mass of the solid content of the entire silicone-based resin in the pressure-sensitive adhesive layer 3. It is more preferably in the range of 0.50 parts by mass or more and 2.00 parts by mass or less, and particularly preferably in the range of 0.70 parts by mass or more and 1.80 parts by mass or less.
  • the content of the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 is less than 0.10 parts by mass in terms of solid content with respect to 100 parts by mass in solid content of the entire silicone-based resin in the pressure-sensitive adhesive layer 3, light such as ultraviolet rays is emitted.
  • the cross-linking / curing (first-step cross-linking reaction) of the silicone-based resin by the thermal polymerization initiator of the pressure-sensitive adhesive layer 3 becomes insufficient at the stage before the irradiation.
  • the pressure-sensitive adhesive layer 3 may be softened due to the silicone gum (G) component.
  • the vibration of the dicing is easily transmitted to the pressure-sensitive adhesive layer 3, and the vibration width becomes large.
  • the semiconductor element substrate may deviate from the reference position.
  • the fragmented semiconductor chips may be chipped (chipping), or that the size of each semiconductor chip may deviate.
  • the adhesive force and tack force of the pressure-sensitive adhesive layer 3 may decrease.
  • the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
  • the silicone-based resin is crosslinked depending on the type of the thermal polymerization initiator and the heating temperature / time before irradiating with light such as ultraviolet rays.
  • the curing first-stage cross-linking reaction
  • the pressure-sensitive adhesive layer 3 may become too hard.
  • the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
  • the thermal polymerization initiator itself or a component derived from the decomposition product of the thermal polymerization initiator may remain on the adherend and contaminate the adherend.
  • the silicone-based pressure-sensitive adhesive layer of the present embodiment is a silicone-based resin in which silicone gum (G) and silicone resin (R) are mixed as main components, and at least two or more in one molecule as a cross-linking agent for the silicone-based resin.
  • the present invention comprises a pressure-sensitive adhesive composition containing an organopolysiloxane having a silicon atom-bonded hydrogen atom (SiH group), a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst.
  • Other components may be contained as long as the effect of the above is not impaired. Examples of other components include a cohesive force improving agent, a reinforcing filler, a peeling control agent, and the like.
  • the cohesive force improver is used as necessary to improve the cohesive force of the pressure-sensitive adhesive layer 3.
  • the cohesive force improving agent is not particularly limited, but for example, a polyfunctional thiol is used.
  • Examples of the cohesive force improving agent composed of polyfunctional thiol include Karenz (registered trademark) MT-PE1 and Karenz MT-NR1 manufactured by Showa Denko KK.
  • the silicone-based resin and the polyfunctional thiol are used. It is necessary to use a compatibilizer with.
  • the compatibilizer is not particularly limited, but for example, KBM-802 and KBM-803 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd., which are silane coupling agents having a mercapto group, and Dow Toray. SH6062 (trade name) manufactured by Co., Ltd. and the like can be mentioned.
  • the amount of the cohesive force improving agent added is preferably in the range of 6 parts by mass or less in terms of solid content with respect to 100 parts by mass in solid content of the entire silicone resin.
  • the amount of the cohesive force improver added exceeds 6 parts by mass in terms of solid content with respect to 100 parts by mass of the solid content of the entire silicone resin, the silicone resin and the cohesive force improver are still present even if the compatibilizer is added. There is a risk of phase separation from the polyfunctional thiol.
  • the reinforcing filler is used, if necessary, in order to improve the strength of the pressure-sensitive adhesive layer 3.
  • the reinforcing filler is not particularly limited, but for example, Aerosil (registered trademark) 130, Aerosil 200, Aerosil 300 manufactured by Nippon Aerosil Co., Ltd., Leoloseal (registered trademark) QS-102 manufactured by Tokuyama Corporation, Leolosil QS-30, DSL. Examples thereof include Carplex (registered trademark) 80 manufactured by Japan Co., Ltd. and Hi-Sil (registered trademark) -233-D manufactured by PPG.
  • the peeling control agent is used as necessary in order to further reduce the adhesive force of the pressure-sensitive adhesive layer 3 after irradiation with light such as ultraviolet rays.
  • the peeling control agent is not particularly limited, and examples thereof include a light peeling additive such as silicone oil. However, if the amount of the peeling control agent added is large, the surface of the adherend may be contaminated by bleeding out, so it is preferable to add the peeling control agent within an acceptable range.
  • the thickness of the pressure-sensitive adhesive layer 3 is preferably in the range of 10 ⁇ m or more and 100 ⁇ m or less, and more preferably in the range of 20 ⁇ m or more and 40 ⁇ m or less.
  • the thickness of the pressure-sensitive adhesive layer 3 is less than 10 ⁇ m, the thickness of the silicone-based pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 3 becomes thin, so that the adhesive strength of the pressure-sensitive adhesive tape 1 tends to decrease.
  • the thickness of the pressure-sensitive adhesive layer 3 is thicker than 100 ⁇ m, cohesive failure of the pressure-sensitive adhesive layer 3 may easily occur.
  • the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1, there is a possibility that adhesive residue is likely to occur on the semiconductor chip or the like.
  • the vibration of the dicing is easily transmitted to the pressure-sensitive adhesive layer 3, and the vibration width becomes large.
  • the semiconductor element substrate may deviate from the reference position.
  • the fragmented semiconductor chips may be chipped (chipping), or that the size of each semiconductor chip may deviate.
  • a base is formed between the base material 2 and the adhesive layer 3 according to the manufacturing conditions of the adhesive tape 1 and the usage conditions of the adhesive tape 1 after production.
  • An anchor coat layer suitable for the type of the material 2 may be provided, or a surface treatment such as a corona treatment may be applied. This makes it possible to improve the adhesion between the base material 2 and the pressure-sensitive adhesive layer 3.
  • the surface of the base material 2 (the surface opposite to the surface facing the pressure-sensitive adhesive layer 3) may be subjected to a surface treatment such as a peelability improving treatment.
  • the treatment agent used for the surface treatment of the base material 2 is not particularly limited, but for example, a long-chain alkyl vinyl monomer polymer, a fluoroalkyl vinyl monomer polymer, a polyvinyl alcohol carbamate, an aminoalkyd resin and the like.
  • Non-silicone-based release treatment agent and the like can be used. Examples of such a non-silicone-based peeling agent include Peroyl (registered trademark) 1050 and Peroyl 1200 manufactured by Lion Specialty Chemicals Co., Ltd.
  • a release liner may be provided on the surface of the pressure-sensitive adhesive layer 3 (the surface opposite to the surface facing the base material 2), if necessary.
  • a film such as paper, polyethylene, polypropylene, polyethylene terephthalate, etc., which has been subjected to a peeling treatment for enhancing the releasability from the silicone-based pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 3 can be used.
  • the material used for the peeling treatment of the peeling liner is not particularly limited, and for example, a material such as fluoroalkyl-modified silicone, a long-chain alkylvinyl monomer polymer, or an aminoalkyd-based resin can be used.
  • the overall thickness of the adhesive tape 1 having the structure as described above is preferably in the range of 20 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the adhesive tape 1 is less than 20 ⁇ m, when the adhesive tape 1 is used for dicing a semiconductor element substrate or the like, it may be difficult to peel off the formed semiconductor chip or the like from the adhesive tape 1. ..
  • the thickness of the adhesive tape 1 exceeds 200 ⁇ m, when the adhesive tape 1 is attached to the semiconductor element substrate, it becomes difficult for the adhesive tape 1 to follow the unevenness formed on the attachment surface of the semiconductor element substrate. In this case, the adhesive area between the adhesive tape 1 and the semiconductor element substrate or the like becomes small, and the semiconductor chip or the like may easily scatter during dicing.
  • the adhesive tape 1 When producing the adhesive tape 1, first, components such as the above-mentioned silicone-based pressure-sensitive adhesive, cross-linking agent, and photosensitive platinum (Pt) catalyst are dissolved in a general-purpose organic solvent such as toluene or ethyl acetate to prepare the pressure-sensitive adhesive. Get the solution. Subsequently, this pressure-sensitive adhesive solution is applied to the surface of the base material 2 which has undergone surface treatment or formation of an anchor coat layer, if necessary, so as to have a predetermined thickness using a comma coater or the like. Next, the base material 2 coated with the pressure-sensitive adhesive solution is heated in a drying furnace to dry and cure the pressure-sensitive adhesive solution to form the pressure-sensitive adhesive layer 3.
  • a general-purpose organic solvent such as toluene or ethyl acetate
  • an anchor coat layer if necessary, so as to have a predetermined thickness using a comma coater or the like.
  • the conditions for heating and drying cannot be unconditionally determined because they depend on the half-life temperature of the thermal polymerization initiator, but for example, the conditions disclosed in Japanese Patent Application Laid-Open No. 2012-107125 can be referred to.
  • the temperature is gradually raised at a temperature of 40 to 90 ° C. in the first half zone portion of the drying furnace to perform initial drying.
  • heat drying may be performed for 1 to 5 minutes in a temperature range of 120 to 200 ° C., and the roll-shaped raw material may be wound up, but this is not the case.
  • the adhesive tape 1 in which the adhesive layer 3 is laminated on the base material 2 is obtained.
  • the pressure-sensitive adhesive layer 3 is in a state in which a part of the silicone-based resin is crosslinked and cured (crosslinking reaction in the first step) by the thermal polymerization initiator.
  • the adhesive tape 1 of the present embodiment is used for dicing a semiconductor material that is a source of a semiconductor chip in a process of manufacturing a semiconductor chip having a semiconductor element such as an LED (Light Emitting Diode) or a power semiconductor.
  • a semiconductor element such as an LED (Light Emitting Diode) or a power semiconductor.
  • the adhesive tape 1 is a semiconductor chip formed by dicing a semiconductor element substrate in which a plurality of semiconductor elements such as LED elements and power semiconductor elements are formed on a substrate made of resin, ceramic, or the like. Used to obtain.
  • a seal is used as an example of a coating material so as to cover the semiconductor element.
  • a stop resin may be provided.
  • the adhesive tape 1 of the present embodiment can be preferably used by dicing a semiconductor device substrate provided with a sealing resin.
  • the following method is conventionally known. First, an adhesive tape for dicing is attached from the substrate side of the semiconductor element substrate, and the semiconductor element substrate is cut from the side where the semiconductor element is formed by a dicer or the like. Then, each semiconductor chip formed by cutting is peeled off from the adhesive tape to obtain a plurality of semiconductor chips.
  • epoxy resins having excellent electrical characteristics and heat resistance have been conventionally used, but epoxy resins are used for high-power LEDs and power semiconductors. If this is the case, there is a problem that the color is easily discolored when used for a short-wavelength LED, or depending on the usage environment of the semiconductor chip.
  • silicone resins are often used as sealing resins for semiconductor elements such as LEDs and power semiconductors because discoloration due to heat or light is less likely to occur compared to epoxy resins. More specifically, a silicone resin containing both or one of a methyl group and a phenyl group as a functional group, that is, a silicone resin containing a methyl group, a silicone resin containing a phenyl group, and both a methyl group and a phenyl group. In many cases, the contained silicone resin is used.
  • the sealing resin for the semiconductor element, discoloration of the sealing resin due to heat or light can be suppressed. Further, the silicone resin has a high light transmittance of 88% or more (wavelength 400 to 800 nm), and the refractive index can be adjusted in the range of 1.41 or more and 1.57 or less. Therefore, when the semiconductor element is an LED, the synchrotron radiation from the LED can be efficiently taken out of the package by using a silicone resin having a higher refractive index as the sealing resin.
  • the refractive index of the encapsulant can be made higher than that in the case of using a silicone resin containing a methyl group. The efficiency of emitted light can be improved.
  • the silicone resin containing a methyl group is not particularly limited, but for example, KER-2300, KER-2460, KER-2500N, KER-2600, KER-2700, KER- of Shin-Etsu Chemical Co., Ltd. 2900, X-32-2528 (all trade names), IVS4312, IVS4312, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, IVSG3445, IVSG0810, IVSG5778, XE13 manufactured by Momentive Performance Materials.
  • the silicone resin containing a methyl group and a phenyl group is not particularly limited, and examples thereof include KER-6075, KER-6150, and KER-6020 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Can be mentioned.
  • the silicone resin containing a phenyl group is not particularly limited, but for example, KER-6110, KER-6000, KER-6200, ASP-1111, ASP-1060, ASP-1120 manufactured by Shin-Etsu Chemical Co., Ltd.
  • an adhesive tape for dicing used for cutting a semiconductor element for example, an adhesive tape in which the adhesive layer is made of an acrylic resin-based adhesive is used.
  • an adhesive tape in which the adhesive layer is made of an acrylic resin-based adhesive is used.
  • the sealing resin and the adhesive tape are obtained. If the adhesive strength of the semiconductor chip is insufficient, problems such as scattering of semiconductor chips during dicing may occur.
  • the above-mentioned silicone resin has a property of higher releasability as compared with, for example, an epoxy resin conventionally used as a sealing resin. Therefore, for example, when an adhesive tape whose adhesive layer is an acrylic resin-based adhesive is attached to a semiconductor element substrate using a silicone resin as a sealing resin, it adheres to the silicone resin which is the sealing resin. Adhesive strength with the tape tends to be small. As a result, problems such as scattering of semiconductor chips are more likely to occur during dicing of the semiconductor element substrate.
  • the adhesive layer 3 is a mixture of silicone gum (G) and silicone resin (R) in an appropriate ratio, and a predetermined amount of silicon atoms.
  • G silicone gum
  • R silicone resin
  • a part of the silicone-based resin is crosslinked and cured by the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 (1). Since it is in the state of being crosslinked at the stage), the semiconductor element substrate is sealed even when it is used by pasting it from the sealing resin side made of silicone resin when dying the semiconductor element substrate.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 contains a photosensitive platinum (Pt) catalyst and a cross-linking agent together with the above-mentioned silicone-based resin, so that the silicone-based resin is irradiated with light such as ultraviolet rays.
  • the photosensitive platinum (Pt) catalyst is activated, and the silicon atom-bonded alkenyl group of the silicone gum (Galk ) in the silicone-based resin and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent for the silicone-based resin. Since the second-stage cross-linking reaction (addition reaction) between the two is promoted and the cross-linking density is increased, the cohesive force of the adhesive is further increased as compared with that before light irradiation such as ultraviolet rays. As a result, the tack force of the pressure-sensitive adhesive layer 3 is appropriately reduced, and the fracture mode in the holding force test is "interfacial peeling" or "does not fall” in the holding force test. As a result, it is possible to realize good pick-up performance when peeling the semiconductor chip or the like from the adhesive tape 1, and it is possible to suppress adhesive residue on the semiconductor chip or the like.
  • 2 (a) to 2 (e) are views showing a method of manufacturing a semiconductor chip using the adhesive tape 1 of the present embodiment.
  • a case where a semiconductor chip having an LED element as a semiconductor element is manufactured by using the adhesive tape 1 will be described as an example.
  • the method described below is an example of a method of using the adhesive tape 1 and a method of manufacturing a semiconductor chip using the adhesive tape 1, and is not limited to the following methods.
  • a plurality of semiconductor elements 102 are mounted on a substrate 101 made of, for example, a resin material or ceramic, to manufacture a semiconductor element substrate 100.
  • the semiconductor element 102 is, for example, an LED element, and although not shown, the semiconductor element 102 is configured by stacking a plurality of semiconductor layers including, for example, a light emitting layer that emits light when energized, and an electrode is formed on the upper portion. ..
  • a plurality of semiconductor elements formed on the substrate 101 of the semiconductor element substrate 100 are sealed with a sealing resin 103 made of a silicone-based resin (sealing step).
  • the plurality of semiconductor elements 102 are collectively sealed with the sealing resin 103, but the individual semiconductor elements 102 may be individually sealed with the sealing resin 103.
  • the adhesive tape 1 and the semiconductor element substrate 100 are bonded together so that the adhesive layer 3 of the adhesive tape 1 faces the sealing resin 103 of the semiconductor element substrate 100 ( Pasting process).
  • the semiconductor element substrate 100 is cut by a dicer or the like along the planned cutting line X in a state where the adhesive tape 1 and the semiconductor element substrate 100 are bonded together. (Cutting process).
  • the semiconductor element substrate 100 to which the adhesive tape 1 is attached is cut from the substrate 101 side.
  • a so-called full cut is performed in which the semiconductor element substrate 100 is completely cut in the thickness direction.
  • the adhesive tape 1 attached to the semiconductor element substrate 100 is irradiated with light such as ultraviolet rays from the base material 2 side (irradiation step).
  • the base material 2 is made of a material that transmits light such as ultraviolet rays. Therefore, by irradiating the adhesive tape 1 with light such as ultraviolet rays from the base material 2 side, the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays through the base material 2.
  • the pressure-sensitive adhesive layer 3 since the pressure-sensitive adhesive layer 3 has a light-sensitive platinum (Pt) catalyst, the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays to obtain a light-sensitive platinum (Pt) catalyst. Is activated, and the second-stage cross-linking reaction (addition reaction) between the silicone-based resin containing the silicon atom-bonded alkenyl group in the pressure-sensitive adhesive layer 3 and the cross-linking agent is promoted. As a result, the crosslink density in the pressure-sensitive adhesive layer 3, that is, the cohesive force is further increased as compared with before irradiation with light such as ultraviolet rays, and the tack force of the pressure-sensitive adhesive layer 3 is reduced.
  • Pt light-sensitive platinum
  • the semiconductor chip 200 formed by cutting the semiconductor element substrate 100 is peeled off (picked up) from the adhesive tape 1, and as shown in FIG. 2E, the semiconductor chip is separated into individual pieces. 200 can be obtained (peeling step).
  • the pressure-sensitive adhesive layer 3 is a mixture of silicone gum (G) and silicone resin (R) in an appropriate ratio, and has a predetermined amount of silicon atom-bonded alkenyl groups. It is composed of a pressure-sensitive adhesive composition containing a silicone-based resin and a thermal polymerization initiator.
  • the adhesive tape 1 of the present embodiment has a good adhesive force and a tack force with respect to the sealing resin 103 made of a silicone resin by having the above-mentioned structure.
  • the adhesive tape 1 of the present embodiment can suppress the scattering of the semiconductor chip 200 when used for dicing the semiconductor element substrate 100.
  • the pressure-sensitive adhesive composition containing the silicone-based resin constituting the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive tape 1 of the present embodiment has good adhesive strength with the sealing resin 103 as described above, while being separated. It has a high type property. That is, the adhesive tape 1 of the present embodiment is a photosensitive platinum that promotes an addition reaction between a silicone-based resin containing a silicon atom-bonded alkenyl group in the adhesive layer 3 and a cross-linking agent by irradiation with light such as ultraviolet rays. Contains (Pt) catalyst.
  • the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays via the base material 2, so that the light-sensitive platinum (Pt) catalyst is activated and the pressure-sensitive adhesive layer 3 is formed.
  • the cross-linking density in the pressure-sensitive adhesive layer 3 is further increased, that is, the cohesive force is further increased as compared with before irradiation with light such as ultraviolet rays. It can be increased and the tack force of the pressure-sensitive adhesive layer 3 can be reduced.
  • the peeling step when the semiconductor chip 200 obtained by dicing the semiconductor element substrate 100 is peeled (picked up) from the adhesive tape 1, the generation of so-called adhesive residue on the semiconductor chip 200 is suppressed. can do. In addition, good pick-up performance when peeling the semiconductor chip 200 from the adhesive tape 1 can be realized.
  • the method for obtaining an individualized semiconductor chip by attaching an adhesive tape 1 to a semiconductor element substrate on which a plurality of semiconductor elements are formed from the sealing resin side and performing dicing is not limited to this.
  • the adhesive tape 1 of the present embodiment is, for example, in the manufacture of a chip scale package LED, in which a plurality of LED elements are diced from a semiconductor material coated with a phosphor as an example of a coating material, and the chip scale is individualized. It may be used to obtain a package LED.
  • the phosphor is a member in which the fluorescent material is dispersed in a resin material, ceramic, or the like.
  • the chip scale package LEDs that have been separated during dicing tend to scatter easily.
  • the adhesive tape 1 of the present embodiment having the above-described configuration, it is possible to maintain good adhesive force between the phosphor and the adhesive layer 3, and the chip scale package is individualized. It is possible to suppress the scattering of LEDs.
  • the adhesive layer 3 is irradiated with light such as ultraviolet rays to reduce the tacking force, so that the chip scale package LED separated from the adhesive tape 1 can be easily peeled off and the peeled chip scale is peeled off. It is possible to suppress the generation of adhesive residue on the package LED.
  • silicone-based resins (a) to (j) are used as the main components of the pressure-sensitive adhesive composition, and the following silicon atom-bonded hydrogen is used as the cross-linking agent.
  • Organopolysiloxanes (organohydrogenpolysiloxanes) (m) and (n) having an atom (SiH) were used.
  • the silicone-based resins (a) to (d) are all a mixture of a silicone gum (Galk ) containing a silicon atom-bonded alkenyl group and a silicone resin (R), and the mixing ratio thereof and the silicon atom-bonded alkenyl group are contained. The amounts are different from each other.
  • a silicone gum (Galk ) a dimethylvinylsiloxy group-blocking dimethylsiloxane / methylvinylsiloxane copolymer having a weight average molecular weight (Mw) of about 500,000 at both ends of the molecular chain was used, and for the silicone resin (R).
  • Organopolysiloxane (MQ resin) having R 2 3 SiO 0.5 unit (M unit) and SiO 2 unit (Q unit) having a weight average molecular weight (Mw) of about 5,000 was used.
  • the silicone-based resins (e) and (f) are both single products of the silicone gum (Galk ) containing a silicon atom-bonded alkenyl group, and the silicon atom-bonded alkenyl group contents are different from each other.
  • the silicone gum (Galk ) of the silicone-based resin (e) a dimethylsiloxane / methylhexenylsiloxane copolymer having a weight average molecular weight (Mw) of about 300,000 at both ends of the molecular chain and dimethylhexenylsiloxy group-sealed is used, and the silicone-based resin (e) is silicone-based.
  • silicone gum (Galk ) of the resin (f) a dimethylvinylsiloxy group-blocked dimethylsiloxane polymer having a weight average molecular weight (Mw) of about 200,000 at both ends of the molecular chain was used.
  • the silicone-based resins (g) to (i) are all a mixture of a silicone gum (G 0 ) and a silicone resin (R) that do not contain a silicon atom-bonded alkenyl group, and the mixing ratios are different from each other.
  • MQ resin Organopolysiloxane having 0.5 units of SiO (M units) and 2 units of SiO (Q units) was used.
  • the silicone-based resin (j) is a single substance of the silicone resin (R), and the silicone resin (R) has a weight average molecular weight (Mw) of about 5,000 in 0.5 units of R 2 3 SiO (R).
  • Mw weight average molecular weight
  • MQ resin Organopolysiloxane having 2 units of SiO (M unit) and 2 units of SiO (Q unit) was used.
  • the alkenyl group content of the silicone resin used above and the SiH group content of the cross-linking agent were quantified by measuring a 1 H-NMR (nuclear magnetic resonance) spectrum at 500 MHz. Specifically, the non-volatile components of the silicone-based resin, was sufficiently dissolved in deuterated chloroform containing dimethylsulfoxide as the internal standard sample, using a JEOL Ltd. NMR apparatus "JNM ⁇ ECA500" (product name) 1 The H-NMR (Nuclear Magnetic Resonance) spectrum was measured.
  • the resonance signal area (integral value) of the dimethyl sulfoxide of the internal standard sample and the resonance signal area (integral value) of the alkenyl group in the measurement spectrum were obtained, and from the ratio, the alkenyl group per 1 g (solid content) of the silicone resin was used. The content was calculated.
  • the SiH group content of the cross-linking agent the 1 H-NMR spectrum was measured in the same manner, and the resonance signal area (integrated value) of the dimethyl sulfoxide of the internal standard sample and the resonance signal area of the SiH group (integrated value) in the measurement spectrum were measured. The integrated value) was obtained, and the content of SiH groups per 1 g (solid content) of the cross-linking agent was calculated from the ratio.
  • the cross-linking agent is internally added to the silicone resin from the beginning, the contents of the alkenyl group and the SiH group may be calculated at the same time from the 1 H-NMR spectrum.
  • the total mass of the silicone gum (G) is the total amount of the "silicone gum (G alk ) of the silicone resin (e)" and the “silicone gum (G 0 ) of the silicone resin (g)". ..
  • the total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (g)” and the “silicone resin (R) of the silicone resin (j)".
  • cross-linking agent (C1) obtained by mixing the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 8.82 / 91.18 is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C1) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C1) had a SiH group content of 4.0 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 ⁇ m after drying was obtained.
  • Example 2 ⁇ Preparation of silicone resin solution>
  • the mass ratio (e) / (h) / (j) of the silicone-based resin (e), the silicone-based resin (h), and the silicone-based resin (j) is 1.19 / 96.99 / 1.82.
  • the silicone-based resin (S2) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S2) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S2) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 40.0 / 60.0, and has an alkenyl group content of 2. It was 4 ⁇ 10 -6 mol / g.
  • the total mass of the silicone gum (G) is the total amount of the “silicone gum (G alk ) of the silicone resin (e)” and the “silicone gum (G 0 ) of the silicone resin (h)". ..
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (h)” and the “silicone resin (R) of the silicone resin (j)".
  • cross-linking agent (C2) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 2.83 / 97.17, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C2) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C2) had a SiH group content of 2.9 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 12 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 10 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 22 ⁇ m after drying was obtained.
  • Example 3 ⁇ Preparation of silicone resin solution> The mass ratio (e) / (g) / (j) of the silicone-based resin (e), the silicone-based resin (g), and the silicone-based resin (j) is 2.09 / 87.26 / 10.65.
  • the silicone-based resin (S3) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S3) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S3) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 45.7 / 54.3, and has an alkenyl group content of 4. It was 2 ⁇ 10 -6 mol / g.
  • the total mass of the silicone gum (G) is the total amount of the “silicone gum (G alk ) of the silicone resin (e)” and the “silicone gum (G 0 ) of the silicone resin (g)". ..
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (g)” and the “silicone resin (R) of the silicone resin (j)".
  • the cross-linking agent (C3) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 9.63 / 90.37, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C3) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C3) had a SiH group content of 4.1 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 40 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 90 ⁇ m after drying was obtained.
  • Example 4 ⁇ Preparation of silicone resin solution> The mass ratio (b) / (e) / (g) of the silicone-based resin (b), the silicone-based resin (e), and the silicone-based resin (g) is 49.51 / 0.97 / 49.52.
  • the silicone-based resin (S4) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S4) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S4) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 43.1 / 56.9, and has an alkenyl group content of 2. It was .8 ⁇ 10 -6 mol / g.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", “silicone gum (G alk)” of the silicone resin (e), and “silicone resin (g alk)”. ) Silicone gum (G 0 ) ”.
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (b)” and the “silicone resin (R) of the silicone resin (g)”.
  • the cross-linking agent (C4) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 5.50 / 94.50, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C4) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C4) had a SiH group content of 3.4 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 125 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 145 ⁇ m after drying was obtained.
  • the mass ratio (b) / (e) / (g) of the silicone-based resin (b), the silicone-based resin (e), and the silicone-based resin (g) is 60.37 / 1.18 / 38.45.
  • the silicone-based resin (S5) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S5) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S5) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 41.5 / 58.5, and has an alkenyl group content of 3. It was 4 ⁇ 10 -6 mol / g.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • g) is the total amount of silicone gum (G 0) ”.
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (b)" and the "silicone resin (R) of the silicone resin (g)”.
  • the mass ratio (b) / (e) / (g) of the silicone-based resin (b), the silicone-based resin (e), and the silicone-based resin (g) is 39.69 / 0.78 / 59.53.
  • the silicone-based resin (S6) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S6) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S6) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 44.4 / 55.6, and has an alkenyl group content of 2. It was 3 ⁇ 10 -6 mol / g.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • g) is the total amount of silicone gum (G 0) ”.
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (b)" and the "silicone resin (R) of the silicone resin (g)”.
  • the mass ratio (a) / (e) / (g) of the silicone-based resin (a), the silicone-based resin (e), and the silicone-based resin (g) is 49.51 / 0.98 / 49.51.
  • the silicone-based resin (S7) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S7) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S7) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 45.5 / 54.5, and has an alkenyl group content of 2. It was .9 ⁇ 10 -6 mol / g.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (a)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • Silicone gum (G 0 ) is the total amount.
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (a)” and the "silicone resin (R) of the silicone resin (g)”.
  • the mass ratio (c) / (e) / (h) / (j) of the silicone-based resin (c), the silicone-based resin (e), the silicone-based resin (h), and the silicone-based resin (j) is 39.46.
  • the silicone resin (S8) mixed so as to be /0.77 / 59.18 / 0.59 is diluted and stirred with toluene to prepare a silicone resin (S8) solution (solid content concentration: 30% by mass). did.
  • This silicone-based resin (S8) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 56.0 / 44.0 and an alkenyl group content of 2.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (c)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • h) is the total amount of silicone gum (G 0) ”.
  • the total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (c)", “silicone resin (R) of silicone resin (h)” and “silicone resin (j)”. It is the total amount with "silicone resin (R)".
  • Example 9 ⁇ Preparation of silicone resin solution>
  • the mass ratio (b) / (e) / (g) / (j) of the silicone-based resin (b), the silicone-based resin (e), the silicone-based resin (g), and the silicone-based resin (j) is 33.14.
  • the silicone-based resin (S9) mixed so as to be /0.07 / 66.29 / 0.50 is diluted and stirred with toluene to prepare a silicone-based resin (S9) solution (solid content concentration: 30% by mass). did.
  • This silicone-based resin (S9) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 44.8 / 55.2, and has an alkenyl group content of 7.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)".
  • g) is the total amount of silicone gum (G 0) ”.
  • the total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (b)", “silicone resin (R) of silicone resin (g)” and “silicone resin (j)”. It is the total amount with "silicone resin (R)".
  • cross-linking agent (C5) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 0.58 / 99.42, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C5) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C5) had a SiH group content of 2.5 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 25 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 63 ⁇ m after drying was obtained.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (c)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • Silicone gum (G 0 ) is the total amount.
  • the total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (c)", “silicone resin (R) of silicone resin (g)” and “silicone resin (j)”. It is the total amount with "silicone resin (R)".
  • cross-linking agent (C6) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 8.04 / 91.9, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C6) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C6) had a SiH group content of 3.8 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 ⁇ m after drying was obtained.
  • the silicone-based resin (S11) solution was prepared as follows, the silicone-based resin (S1) solution was changed to the silicone-based resin (S11) solution, and a cross-linking agent and an organic peroxide were added in the preparation of the pressure-sensitive adhesive solution. Instead, the amount of the solution of the photosensitive platinum (Pt) catalyst was changed to 5.33 parts by mass (0.80 parts by mass in terms of solid content), and the thickness of the pressure-sensitive adhesive layer 3 after drying was changed to 35 ⁇ m. An adhesive tape 1 having a total thickness of 73 ⁇ m after drying was obtained in the same manner as in Example 1.
  • silicone resin (S11) which is a mixture of the silicone resin (a) and the silicone resin (f) so that the mass ratio (a) / (f) is 99.90 / 0.10, is diluted with toluene.
  • the mixture was stirred to prepare a silicone resin (S11) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S11) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 40.1 / 59.9, and has an alkenyl group content of 4. It was 7 ⁇ 10 -6 mol / g.
  • the total mass of the silicone gum (G) is the total amount of the “silicone gum (G alk ) of the silicone resin (a)” and the “silicone gum (G alk ) of the silicone resin (f)". ..
  • the total mass of the silicone resin (R) is the amount of the silicone resin (R) of the silicone resin (a).
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • g) is the total amount of silicone gum (G 0) ”.
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (b)" and the "silicone resin (R) of the silicone resin (g)”.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 ⁇ m after drying was obtained.
  • silicone resin (S13) which is a mixture of the silicone resin (e) and the silicone resin (h) so that the mass ratio (e) / (h) is 0.26 / 99.74, is diluted with toluene.
  • the mixture was stirred to prepare a silicone resin (S13) solution (solid content concentration: 30% by mass).
  • This silicone-based resin (S13) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 40.2 / 59.8, and has an alkenyl group content of 5. It was 2 ⁇ 10 -7 mol / g.
  • the total mass of the silicone gum (G) is the total amount of the “silicone gum (G alk ) of the silicone resin (e)" and the “silicone gum (G 0 ) of the silicone resin (h)". ..
  • the total mass of the silicone resin (R) is the amount of the silicone resin (R) of the silicone resin (h).
  • the cross-linking agent (C7) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 1.15 / 98.85, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C7) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C7) had a SiH group content of 2.6 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 ⁇ m after drying was obtained.
  • the total mass of the silicone gum (G) is the total amount of the “silicone gum (G alk ) of the silicone resin (e)” and the “silicone gum (G 0 ) of the silicone resin (i)". ..
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (i)” and the “silicone resin (R) of the silicone resin (j)".
  • cross-linking agent (C8) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 14.88 / 85.12, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C8) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C8) had a SiH group content of 5.0 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 ⁇ m after drying was obtained.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • h) is the total amount of silicone gum (G 0) ”.
  • the total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (b)", “silicone resin (R) of silicone resin (h)” and “silicone resin (j)”. It is the total amount with "silicone resin (R)".
  • cross-linking agent (C9) which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 4.19 / 95.81, is diluted with toluene.
  • the mixture was stirred to prepare a cross-linking agent (C9) solution (solid content concentration: 20% by mass).
  • This cross-linking agent (C9) had a SiH group content of 3.1 ⁇ 10 -3 mol / g.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 30 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 68 ⁇ m after drying was obtained.
  • the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (d)", “silicone gum (G alk ) of the silicone resin (e)", and “silicone resin (G alk)”.
  • Silicone gum (G 0 ) is the total amount.
  • the total mass of the silicone resin (R) is the total amount of the “silicone resin (R) of the silicone resin (d)” and the “silicone resin (R) of the silicone resin (i)”.
  • this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace.
  • the pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 ⁇ m after drying.
  • a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 ⁇ m after drying was obtained.
  • Tables 1 to 3 show the layer structure and the composition of the pressure-sensitive adhesive layer 3 in the pressure-sensitive adhesive tapes 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6.
  • Adhesive strength test (before UV irradiation) Adhesive Tapes 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6 have adhesive strength against BA-SUS in accordance with the method described in the adhesive tape / adhesive sheet test method (JIS Z 0237 (2009)). A test (peeling adhesive strength test) was performed.
  • the adhesive tape 1 from which the release liner has been peeled off is attached to a stainless steel plate (SUS304) having a surface roughness (Ra) of 50 ⁇ 25 nm treated with bright annealing (BA), and a roller having a mass of 2000 g is attached to a roller having a mass of 5 mm / s. It was reciprocated once at a speed and crimped. Then, after leaving it to stand for 20 to 40 minutes, it was peeled off from the stainless steel plate at a speed of 5 mm / s in the 180 ° direction using a tensile tester, and the adhesive strength to the polished SUS plate was measured.
  • SUS304 stainless steel plate having a surface roughness (Ra) of 50 ⁇ 25 nm treated with bright annealing (BA)
  • Ra roller having a mass of 2000 g is attached to a roller having a mass of 5 mm / s. It was reciprocated once at a speed and crimped. Then, after leaving
  • the adhesive strength test was performed on the adhesive tape 1 before it was irradiated with ultraviolet rays (UV). Further, as a result of the adhesive strength test, considering the fixing force when the adhesive tape 1 is used for dicing a semiconductor material, it is preferably 2.4 N / 10 mm or more, and a semiconductor chip or the like individualized by dicing or the like. From the viewpoint of pick-up property, it is preferably 5.5 N / 10 mm or less. More preferably, it is 2.8 N / 10 mm or more and 5.5 N / 10 mm or less.
  • Ball tack test (2-1) Initial (before UV irradiation) Ball tack measurement Adhesive tape / adhesive tape 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 before UV irradiation. The ball tack test was performed according to the method described in the sheet test method (JIS Z 0237 (2009)).
  • the UV irradiation was performed by using a high-pressure mercury lamp and adjusting the UV having a wavelength of 365 nm so that the integrated light intensity was 1200 mJ / cm 2. Although was similarly measured for the ball tack when the cumulative amount of light with 3000 mJ / cm 2, the difference between the case where the cumulative amount of light with 1200 mJ / cm 2 was observed, here, the integrated light quantity of 1200 mJ / It was evaluated as cm 2.
  • the ball tack after UV irradiation (ball No.) was compared with the initial (before UV irradiation) ball tack (ball No.).
  • the adhesive tape 1 was held under the condition of 33% RH, and the elapsed time (falling time (minutes)) until the adhesive tape 1 was peeled off from the stainless steel plate and dropped was measured. Further, the fracture mode when the adhesive tape 1 was peeled off from the stainless steel plate (whether the fracture mode between the adhesive layer 3 and the stainless steel plate was interfacial peeling or cohesive fracture) was observed. The drop time in the holding force test was measured up to 2880 minutes. Further, as a result of the holding force test shown in Tables 4 to 6 described later, the drop time (minutes) and the breaking mode of the adhesive tape 1 are shown.
  • FIG. 3 is a schematic view showing the relationship between the crosslink density of the silicone-based resin in the pressure-sensitive adhesive layer 3 and the result (falling time) of the holding force test of the pressure-sensitive adhesive tape 1.
  • the breaking mode of the adhesive tape 1 with respect to the stainless steel plate by the holding force test is changed to [Aggregation of the adhesive layer 3]. It changes in the order of [break (fall)] ⁇ [hold (do not fall)] ⁇ [intersection peeling (fall) between the adhesive layer 3 and the stainless steel plate].
  • the holding force (falling time) of the adhesive tape 1 increases as the cross-linking density of the silicone-based resin in the adhesive layer 3 increases. To rise.
  • the holding force (falling time) of the adhesive tape 1 increases as the cross-linking density of the silicone-based resin in the adhesive layer 3 increases. descend. This is because the cohesive force of the adhesive layer 3 increases as the cross-linking density of the silicone-based resin increases, the adhesive force of the adhesive tape 1 decreases, and as a result, the adhesive tape easily peels off from the stainless steel plate and falls off. It is presumed that this is the reason.
  • At least the destruction mode after UV irradiation is preferably retention or interfacial peeling, and at least the destruction mode after UV irradiation is more preferably interfacial peeling, and the initial (before UV irradiation) and It is more preferable that both destruction modes after UV irradiation are interfacial peeling.
  • the drop time is the initial (before UV irradiation) when the adhesive tape 1 is used for dicing the semiconductor material.
  • the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1, the adhesive tape 1 is irradiated with UV to leave adhesive residue on the semiconductor chip or the like. It is less likely to occur.
  • the adhesive tape 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6 was subjected to an adhesive residue test on a silicone resin.
  • agent A and agent B of a silicone resin containing a methyl group (KER-2500N (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone resin for LED devices, are mixed at a mixing ratio of 1: 1 to prepare a mixed solution.
  • This mixed solution was applied to a stainless steel plate and heated and cured under the conditions of 100 ° C. ⁇ 1 hour and further 150 ° C. ⁇ 2 hours to prepare a silicone test piece A.
  • the A agent and the B agent of a silicone resin containing a phenyl group (KER-6110 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone resin for LED devices, are mixed at a mixing ratio of 3: 7.
  • a mixed solution was prepared. This mixed solution was applied to a stainless steel plate and heated and cured under the conditions of 100 ° C. ⁇ 2 hours and further 150 ° C. ⁇ 5 hours to prepare a silicone test piece B.
  • the release liner of the adhesive tape 1 was peeled off, the adhesive layer 3 was attached to the silicone test pieces A and B, respectively, and a roller having a mass of 2000 g was reciprocated once at a speed of 5 mm / s and crimped.
  • UV is irradiated from the base material 2 side of the adhesive tape 1 in the same manner as described in the measurement of ball tack after UV irradiation, and then left in an environment of a temperature of 40 ° C. and a humidity of 90% RH for 120 hours. did.
  • the adhesive tape 1 was peeled off at a speed of 800 mm / s to 1200 mm / s in the 90 ° direction with respect to the silicone test pieces A and B, and the adhesive residue on the silicone test pieces A and B was visually confirmed. ..
  • Adhesive Residual Test Against Epoxy Resin The adhesive tape 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6 was subjected to an adhesive residue test on an epoxy resin.
  • the agent layer 3 was attached, and a roller having a mass of 2000 g was reciprocated once at a speed of 5 mm / s and pressure-bonded.
  • UV is irradiated from the base material 2 side of the adhesive tape 1 in the same manner as described in the measurement of ball tack after UV irradiation, and then left in an environment of a temperature of 40 ° C. and a humidity of 90% RH for 120 hours. did. Then, at room temperature, the adhesive tape 1 was peeled off from the epoxy test piece in the 90 ° direction at a speed of 800 mm / s to 1200 mm / s, and the adhesive residue on the epoxy test piece was visually confirmed.
  • the anti-silicone resin adhesive residue test and the anti-epoxy resin adhesive residue test were evaluated according to the following criteria.
  • the evaluation of A or B was accepted.
  • Adhesive residue is seen in the range D: Adhesive residue is seen in the range of 5% or more per unit area of the test piece, or glue residue is seen at the edge part of the test piece.
  • the adhesive layer 3 of the adhesive tape 1 from which the release liner was peeled off was attached to the dicing ring, and after cutting off the portion protruding from the ring, a fluorine-based release film (SS1A (trade name) manufactured by Nippa Corporation), It was bonded to a thickness of 75 ⁇ m).
  • a roller having a mass of 2000 g was reciprocated to crimp the adhesive tape 1 and the ring portion.
  • the fluorine-based release film was peeled off, and the dicing test piece was attached to the pressure-sensitive adhesive layer 3 at the center of the ring and pressure-bonded.
  • a dicing test piece was cut into a 10 mm ⁇ 10 mm chip together with the adhesive tape 1 with a dicing blade manufactured by Disco Corporation. .. At this time, the number of scattered chips was measured and the fixing force in the dicing test was evaluated. Subsequently, the adhesive tape 1 attached to the chip pieced into pieces of 10 mm ⁇ 10 mm was irradiated with UV in the same conditions as described in the measurement of ball tack after UV irradiation.
  • the individualized chips were picked up from the adhesive tape 1, and the presence or absence of adhesive residue on the chip was visually confirmed to evaluate the adhesive residue in the dicing test.
  • the number of chips that failed to be picked up was measured to evaluate the pick-up property in the dicing test.
  • the fixing force in the dicing test was evaluated according to the following criteria.
  • the evaluation of A or B was accepted.
  • the adhesive residue in the dicing test was evaluated according to the following criteria. The evaluation of A was passed. A: No adhesive residue is seen on the tip D: Adhesive residue is seen on the tip, or adhesive threading is seen on the side of the tip.
  • the pick-up property in the dicing test was evaluated according to the following criteria. The evaluation of A or B was accepted. A: 0 out of 100 chips failed to pick up B: 1 out of 100 chips failed to pick up C: 2 out of 100 chips failed to pick up D: failed to pick up 3 or more out of 100 chips
  • Test Results Tables 4 to 6 show the evaluation results for the adhesive tape 1 of Examples 1 to 10 and Comparative Examples 1 to 6.
  • the adhesive tape 1 of Examples 1 to 10 is useful as an adhesive tape for dicing of a semiconductor material, more specifically, an adhesive tape for dicing which is attached from the sealing resin side of the semiconductor element substrate and used for dicing. It was confirmed that.
  • Examples 5, 7 and 10 in which the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 2.9 ⁇ 10 -6 mol / g or more and 4.1 ⁇ 10 -6 mol / g or less.
  • the adhesive tape 1 of No. 1 had better evaluation results in all the test items than the adhesive tape 1 of the other examples.
  • the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) of Examples 5, 7 and 10 is 41.5 / 58.5 to 50.4 / 49. It was in the range of 0.6.
  • the adhesive tapes 1 of Comparative Examples 1 to 6 in which the pressure-sensitive adhesive layer 3 does not satisfy the requirements of the present invention are subjected to a silicone resin adhesive residue test, an epoxy resin adhesive residue test, and dicing. In the tests (fixing force, adhesive residue and pick-up property), it was confirmed that any of the test results was inferior to that of Examples 1 to 10.
  • the cross-linking reaction of the silicone-based resin does not occur even if it is heated or UV-irradiated.
  • the cohesive force was insufficient. Therefore, a large amount of adhesive residue was observed in the silicone resin adhesive residue test, the epoxy resin adhesive residue test, and the epoxy resin adhesive residue test for confirming practicality.
  • the dicing test since the increase in the cohesive force after UV irradiation was not observed as described above, the pick-up property of the chip of the dicing test piece was inferior, and adhesive residue was observed on the chip.
  • the cohesive force increases in the initial stage before UV irradiation.
  • the cohesive force did not increase even after UV irradiation, and no change was observed in the results of the ball tack test and the holding force test before and after UV irradiation. Therefore, a large amount of adhesive residue was observed in the silicone resin adhesive residue test and the epoxy resin adhesive residue test.
  • the pick-up property of the chip of the dicing test piece was slightly inferior, and a little adhesive residue was observed on the chip.
  • a ball tack test and a ball tack test are performed before and after UV irradiation. No change was observed in the results of the holding power test, and the effect of increasing the cohesive power of the pressure-sensitive adhesive layer 3 by UV irradiation was insufficient. Therefore, a large amount of adhesive residue was observed in the silicone resin adhesive residue test and the epoxy resin adhesive residue test. Also, in the dicing test, the pick-up property of the chip of the dicing test piece was inferior, and adhesive residue was observed on the chip.
  • the dicing test piece is fixed in the dicing test.
  • the force was low, and many chips were scattered during dicing.
  • This is a step before UV irradiation, that is, a heating / drying step for forming the pressure-sensitive adhesive layer 3 on the base material 2, and a cross-linking reaction of the silicone gum (G) of the silicone-based resin already in the pressure-sensitive adhesive layer 3. It is presumed that this was due to the progress of the thermal polymerization initiator, which was cured and became too hard. No adhesive residue was found in the silicone resin adhesive residue test and the epoxy resin adhesive residue test. Also, in the dicing test, no adhesive residue was found on the chips that did not scatter.
  • the adhesive layer Since there are many silicone resins (R) that hardly contribute to the cross-linking of No. 3, the effect of increasing the cohesive force of the pressure-sensitive adhesive layer 3 by UV irradiation was insufficient. Therefore, in the anti-silicone resin adhesive residue test and the anti-epoxy resin adhesive residue test, a slightly large amount of adhesive residue was observed. Also, in the dicing test, the pick-up property of the chip of the dicing test piece was slightly inferior, and a little adhesive residue was observed on the chip.
  • Adhesive tape 1 ... Adhesive tape, 2 ... Base material, 3 ... Adhesive layer, 100 ... Semiconductor element substrate, 101 ... Substrate, 102 ... Semiconductor element, 103 ... Encapsulating resin, 200 ... Semiconductor chip

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Abstract

This adhesive tape for dicing comprises a base material and an adhesive layer. The adhesive layer comprises an adhesive composition containing: a silicone-based resin in which a silicone gum (G) and a silicone resin (R) are mixed; an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule as a crosslinking agent; a peroxide as a thermal polymerization initiator; and a photosensitive platinum (Pt) catalyst. The mixing ratio of the silicone gum (G) and the silicone resin (R) falls within the range of 40.0/60.0 to 56.0/44.0. The silicone gum (G) includes a silicone gum (Galk) comprising an organopolysiloxane containing a silicon atom-bonded alkenyl group, with the content of silicon atom-bonded alkenyl groups falling within the range of 7.0×10-7 to 5.5×10-6 mol/g.

Description

ダイシング用粘着テープおよび半導体チップの製造方法Manufacturing method of adhesive tape for dicing and semiconductor chip
　本発明は、半導体チップの材料となる半導体材料のダイシングに用いられるダイシング用粘着テープ、およびダイシング用粘着テープを使用した半導体チップの製造方法に関する。 The present invention relates to an adhesive tape for dicing used for dicing a semiconductor material used as a material for a semiconductor chip, and a method for manufacturing a semiconductor chip using the adhesive tape for dicing.
　従来、ＬＥＤ（Light Emitting Diode）等を有する半導体チップを作製するために使用されるダイシング用粘着テープとして、アクリル系樹脂からなる接着剤層を有する粘着テープが知られている（特許文献１参照）。
　また、ＬＥＤ等を有する半導体チップを作製するために使用されるダイシング用粘着テープとして、シリコーン系樹脂からなる粘着剤層を有する粘着テープが知られている（特許文献２、特許文献３参照）。
　さらに、ダイシング用粘着テープを使用して半導体チップを作製する方法としては、基板上に複数の半導体素子が形成された半導体素子基板の基板側に粘着テープを貼り付け、ダイサーにより半導体素子基板を切断する方法が知られている（特許文献４参照）。 Conventionally, as an adhesive tape for dicing used for manufacturing a semiconductor chip having an LED (Light Emitting Diode) or the like, an adhesive tape having an adhesive layer made of an acrylic resin is known (see Patent Document 1). ..
Further, as an adhesive tape for dicing used for producing a semiconductor chip having an LED or the like, an adhesive tape having an adhesive layer made of a silicone-based resin is known (see Patent Documents 2 and 3).
Further, as a method of manufacturing a semiconductor chip using an adhesive tape for dicing, an adhesive tape is attached to the substrate side of a semiconductor element substrate in which a plurality of semiconductor elements are formed on the substrate, and the semiconductor element substrate is cut by a dicer. A method is known (see Patent Document 4).
特開２０１３－３８４０８号公報Japanese Unexamined Patent Publication No. 2013-388408 特開２０１５－０５０２１６号公報Japanese Unexamined Patent Publication No. 2015-05216 特開２０１６－１２２８１２号公報Japanese Unexamined Patent Publication No. 2016-122812 特開２００５－９３５０３号公報Japanese Unexamined Patent Publication No. 2005-93503
　ところで、近年、ダイシングにより個片化された半導体チップを作製する方法として、複数の半導体素子が封止樹脂や蛍光体等の被覆材に被覆された半導体材料に粘着テープを貼り付けてダイシングを行う技術、所謂、ウエハーレベルＣＳＰ（チップ・スケール・パッケージ）プロセスに対応した技術が提案されている。
　このように、半導体素子が被覆材に被覆された半導体材料に粘着テープを貼り付ける場合、粘着テープにおける粘着剤層の構成や被覆材の素材等によっては、粘着力が不足して、ダイシングにより個片化された半導体チップが飛散する場合がある。また、半導体チップの飛散を抑制するために粘着剤層のボールタックや粘着力を高く設計すると、得られた半導体チップを粘着テープから剥離した際に、粘着剤が半導体チップに付着したまま残存する所謂糊残りが生じる場合がある。 By the way, in recent years, as a method for producing a semiconductor chip individualized by dicing, an adhesive tape is attached to a semiconductor material in which a plurality of semiconductor elements are coated with a coating material such as a sealing resin or a phosphor, and dicing is performed. Technologies corresponding to so-called wafer level CSP (chip scale package) processes have been proposed.
In this way, when the adhesive tape is attached to the semiconductor material in which the semiconductor element is coated with the coating material, the adhesive strength is insufficient depending on the composition of the adhesive layer in the adhesive tape, the material of the coating material, etc. The fragmented semiconductor chip may scatter. Further, if the ball tack and adhesive strength of the adhesive layer are designed to be high in order to suppress the scattering of the semiconductor chip, when the obtained semiconductor chip is peeled from the adhesive tape, the adhesive remains attached to the semiconductor chip. So-called adhesive residue may occur.
　本発明は、被覆材で被覆された複数の半導体素子を有する半導体材料に対して良好な粘着力およびタック力を有するとともに、ダイシングにより個片化された半導体チップを剥離した場合に半導体チップに対する糊残りが抑制されたダイシング用粘着テープ、およびこれを用いた半導体チップの製造方法を提供することを目的とする。 The present invention has good adhesive force and tack force to a semiconductor material having a plurality of semiconductor elements coated with a coating material, and glue to the semiconductor chip when the semiconductor chip separated by dicing is peeled off. It is an object of the present invention to provide an adhesive tape for dicing in which the remainder is suppressed, and a method for manufacturing a semiconductor chip using the adhesive tape.
　本発明者らは、かかる目的のもと、ダイシング用粘着テープの粘着剤層について鋭意検討した結果、粘着剤層を、少なくとも（１）ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンから成るシリコーンガムを含むシリコーン系樹脂と、（２）ケイ素原子結合水素原子（ＳｉＨ基）を有する架橋剤と、（３）過酸化物からなる熱重合開始剤と、を含む特定の樹脂組成物に対して、さらに（４）光感応白金（Ｐｔ）触媒を添加した粘着剤組成物から構成し、シリコーン系樹脂におけるシリコーンガムとシリコーンレジンとの混合比率、ならびにシリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量を所定の範囲とすれば、被覆材で被覆された複数の半導体素子を有する半導体材料に対して安定且つ良好な粘着力を有するとともに、ダイシングにより個片化された半導体チップを剥離した場合に半導体チップに対する糊残りが抑制されることを見出し、本発明をなすに至った。
　すなわち、ダイシング用粘着テープの粘着剤層を、シリコーンガムとシリコーンレジンとが所定の比率で混合され、且つ所定量のケイ素原子結合アルケニル基を有するシリコーン系樹脂に対して、架橋剤と熱重合開始剤と光感応白金（Ｐｔ）触媒とを添加した粘着組成物から構成することで、以下の効果を奏することを見出した。まず、被覆材で被覆された複数の半導体素子を有する半導体材料を複数の半導体チップに分割する際には、粘着剤層が、該粘着剤層を基材上に形成するための加熱・乾燥工程を経た際に、熱重合開始剤によりシリコーン系樹脂の一部が架橋・硬化（１段階目の架橋反応）された状態になっているため、該粘着剤層の適度な凝集力がもたらす安定且つ良好なタック力および粘着力により、ダイシング時に個片化された半導体チップが飛散することが抑制されることを見出した。またその一方で、ダイシングにより個片化された半導体チップをダイシング用粘着テープから剥離する際には、紫外線等の光を粘着剤層に照射することで、粘着剤組成物中の光感応白金（Ｐｔ）触媒が活性化され、シリコーン系樹脂中のシリコーンガムが有するケイ素原子結合アルケニル基と架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間で２段階目の架橋反応（付加反応）が促進され、架橋密度がさらに高くなるので、粘着剤組成物の凝集力が光照射前と比較してさらに大きくなる。この結果、粘着剤層のタック力が適切に低下し、さらに保持力試験における破壊モードが「界面剥離」あるいは保持力試験において「落下しない」ものとなる。これにより、半導体チップのダイシング用粘着テープからのピックアップ性が良好となり、また半導体チップに対する糊残りが抑制されることを見出した。 For this purpose, the present inventors have diligently studied the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape for dicing, and as a result, the pressure-sensitive adhesive layer is a silicone gum composed of at least (1) an organopolysiloxane containing a silicon atom-bonded alkenyl group. For a specific resin composition containing a silicone-based resin containing, (2) a cross-linking agent having a silicon atom-bonded hydrogen atom (SiH group), and (3) a thermal polymerization initiator composed of a peroxide. Further (4) composed of a pressure-sensitive adhesive composition to which a photosensitive platinum (Pt) catalyst is added, the mixing ratio of silicone gum and silicone resin in the silicone-based resin, and the content of silicon atom-bonded alkenyl groups in the entire silicone-based resin. When is within a predetermined range, it has stable and good adhesive strength with respect to a semiconductor material having a plurality of semiconductor elements coated with a coating material, and is a semiconductor when the semiconductor chip separated by dying is peeled off. It has been found that the adhesive residue on the chip is suppressed, and the present invention has been made.
That is, the pressure-sensitive adhesive layer of the adhesive tape for dicing is thermally polymerized with a cross-linking agent on a silicone-based resin in which silicone gum and silicone resin are mixed in a predetermined ratio and have a predetermined amount of silicon atom-bonded alkenyl groups. It has been found that the following effects can be obtained by composing the pressure-sensitive adhesive composition to which the agent and the photosensitizing platinum (Pt) catalyst are added. First, when a semiconductor material having a plurality of semiconductor elements coated with a coating material is divided into a plurality of semiconductor chips, the pressure-sensitive adhesive layer is a heating / drying step for forming the pressure-sensitive adhesive layer on a substrate. Since a part of the silicone-based resin is cross-linked and cured (first-stage cross-linking reaction) by the thermal polymerization initiator, the adhesive layer is stable and has an appropriate cohesive force. It has been found that good tacking force and adhesive force suppress the scattering of the fragmented semiconductor chips during dicing. On the other hand, when the semiconductor chip individualized by dying is peeled off from the adhesive tape for dying, the pressure-sensitive adhesive layer is irradiated with light such as ultraviolet rays, so that the light-sensitive platinum in the pressure-sensitive adhesive composition ( Pt) The catalyst is activated, and the second-step cross-linking reaction (addition reaction) between the silicon atom-bonded alkenyl group of the silicone gum in the silicone-based resin and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent. Is promoted and the crosslink density is further increased, so that the cohesive force of the pressure-sensitive adhesive composition is further increased as compared with that before light irradiation. As a result, the tack force of the pressure-sensitive adhesive layer is appropriately reduced, and the fracture mode in the holding force test is "interfacial peeling" or "does not fall" in the holding force test. As a result, it has been found that the pick-up property of the semiconductor chip from the adhesive tape for dicing is improved, and the adhesive residue on the semiconductor chip is suppressed.
　本発明のダイシング用粘着テープは、基材と当該基材に積層される粘着剤層とを備え、被覆材で被覆された複数の半導体素子を有する半導体材料を、複数の半導体チップに分割する際に使用されるダイシング用粘着テープであって、前記粘着剤層は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが混合されたシリコーン系樹脂、当該シリコーン系樹脂に対する架橋剤として１分子中に少なくとも２個以上のケイ素原子結合水素原子（ＳｉＨ基）を有するオルガノポリシロキサン、熱重合開始剤として過酸化物、および光感応白金（Ｐｔ）触媒を含む粘着剤組成物からなり、前記シリコーン系樹脂全体におけるシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が、質量比で４０．０／６０．０～５６．０／４４．０の範囲であり、前記シリコーンガム（Ｇ）が、ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）を含み、前記シリコーン系樹脂全体における前記ケイ素原子結合アルケニル基の含有量が、７．０×１０-7ｍｏｌ／ｇ以上５．５×１０-6ｍｏｌ／ｇ以下の範囲であることを特徴とするダイシング用粘着テープである。
　ここで、複数の前記半導体素子がシリコーン樹脂からなる前記被覆材により封止された前記半導体材料に対して、当該被覆材側から貼り付けられて使用されることを特徴とすることができる。
　また、前記粘着剤層は、前記粘着剤組成物に含まれる前記シリコーン系樹脂全体における前記ケイ素原子結合アルケニル基の含有量（総量）に対する、当該粘着剤組成物に含まれる前記架橋剤の前記ケイ素原子結合水素原子（ＳｉＨ基）の含有量（総量）のモル比率（ＳｉＨ基／ケイ素原子結合アルケニル基）が、２．０以上１０．０以下の範囲であることを特徴とすることができる。
　また、前記粘着剤層は、前記粘着剤組成物における前記過酸化物の含有量が、前記シリコーン系樹脂全体の固形分１００質量部に対し、固形分で０．１０質量部以上３．００質量部以下の範囲であることを特徴とすることができる。
　また、前記粘着剤層は、前記過酸化物がジアシルパーオキサイド類であることを特徴とすることができる。
　また、前記粘着剤層は、前記粘着剤組成物における前記光感応白金（Ｐｔ）触媒の含有量が、前記シリコーン系樹脂全体の固形分１００質量部に対し、固形分で０．１０質量部以上３．００質量部以下の範囲であることを特徴とすることができる。
　また、前記粘着剤層は、前記シリコーン系樹脂全体における前記ケイ素原子結合アルケニル基の含有量が、２．９×１０-6ｍｏｌ／ｇ以上４．１×１０-6ｍｏｌ／ｇ以下の範囲であることを特徴とすることができる。
　また、ＪＩＳ　Ｚ　０２３７（２００９）に準拠した粘着特性において下記条件（ａ）～（ｃ）の全てを満たすことを特徴とすることができる。
（ａ）ＢＡ－ＳＵＳ試験板に対する光照射前の粘着力は、２．８Ｎ／１０ｍｍ以上５．５Ｎ／１０ｍｍ以下の範囲であることである。
（ｂ）傾斜式ボールタック試験（傾斜角３０°、温度２３℃、相対湿度５０％ＲＨ）におけるボールナンバーの値は、光照射前のボールナンバーの値をＢＮ０、光照射後のボールナンバーの値をＢＮ１とした場合に、ＢＮ０＞ＢＮ１の関係であることである。
（ｃ）光照射後の保持力試験（温度４０℃、相対湿度３３％ＲＨ、放置時間２８８０分）において、落下時の破壊現象は、前記粘着剤層とＢＡ－ＳＵＳ試験板との界面剥離であること、もしくは、当該保持力試験において落下しないことである。 The adhesive tape for dying of the present invention includes a base material and an adhesive layer laminated on the base material, and when a semiconductor material having a plurality of semiconductor elements coated with a coating material is divided into a plurality of semiconductor chips. The pressure-sensitive adhesive layer is a silicone-based resin in which silicone gum (G) and silicone resin (R) are mixed, and is contained in one molecule as a cross-linking agent for the silicone-based resin. The silicone-based resin comprises an organopolysiloxane having at least two or more silicon atom-bonded hydrogen atoms (SiH groups), a peroxide as a thermal polymerization initiator, and a light-sensitive platinum (Pt) catalyst. The mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) in the whole is in the range of 40.0 / 60.0 to 56.0 / 44.0 in terms of mass ratio. The silicone gum (G) contains a silicone gum (G alk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group, and the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is 7. It is an adhesive tape for dying characterized in that it is in the range of 0 × 10 -7 mol / g or more and 5.5 × 10 -6 mol / g or less.
Here, it can be characterized that a plurality of the semiconductor elements are attached to the semiconductor material sealed with the coating material made of a silicone resin from the coating material side and used.
Further, the pressure-sensitive adhesive layer is the silicon of the cross-linking agent contained in the pressure-sensitive adhesive composition with respect to the content (total amount) of the silicon atom-bonded alkenyl groups in the entire silicone-based resin contained in the pressure-sensitive adhesive composition. It can be characterized in that the molar ratio (SiH group / silicon atom-bonded alkenyl group) of the content (total amount) of the atomic-bonded hydrogen atom (SiH group) is in the range of 2.0 or more and 10.0 or less.
Further, in the pressure-sensitive adhesive layer, the content of the peroxide in the pressure-sensitive adhesive composition is 0.10 parts by mass or more and 3.00 parts by mass in terms of solid content with respect to 100 parts by mass of solid content of the entire silicone-based resin. It can be characterized by having a range of less than a part.
Further, the pressure-sensitive adhesive layer can be characterized in that the peroxide is a diacyl peroxide.
Further, in the pressure-sensitive adhesive layer, the content of the photosensitive platinum (Pt) catalyst in the pressure-sensitive adhesive composition is 0.10 parts by mass or more in terms of solid content with respect to 100 parts by mass of solid content of the entire silicone-based resin. It can be characterized in that it is in the range of 3.00 parts by mass or less.
Further, in the pressure-sensitive adhesive layer, the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 2.9 × 10 -6 mol / g or more and 4.1 × 10 -6 mol / g or less. It can be characterized by being.
Further, it can be characterized in that all of the following conditions (a) to (c) are satisfied in the adhesive characteristics conforming to JIS Z 0237 (2009).
(A) The adhesive strength of the BA-SUS test plate before light irradiation is in the range of 2.8 N / 10 mm or more and 5.5 N / 10 mm or less.
(B) The ball number values in the tilted ball tack test (tilt angle 30 °, temperature 23 ° C., relative humidity 50% RH) are the ball number value before light irradiation as BN0 and the ball number value after light irradiation. Is BN1, and the relationship is BN0> BN1.
(C) In the holding power test after light irradiation (temperature 40 ° C., relative humidity 33% RH, leaving time 2880 minutes), the fracture phenomenon at the time of dropping is the interface peeling between the adhesive layer and the BA-SUS test plate. There is, or it does not fall in the holding force test.
　また、他の観点から捉えると、本発明が適用される半導体チップの製造方法は、上記のダイシング用粘着テープを、シリコーン樹脂からなる封止樹脂で封止された複数の前記半導体素子が基板上に形成された半導体素子基板に対して、当該封止樹脂側から貼り付ける貼付工程と、前記ダイシング用粘着テープが貼り付けられた前記半導体素子基板を、複数の半導体チップに切断する切断工程と、前記半導体素子基板の前記ダイシング用粘着テープに光を照射する照射工程と、前記複数の半導体チップから、前記ダイシング用粘着テープを剥がす剥離工程とを含む半導体チップの製造方法である。 From another point of view, in the method for manufacturing a semiconductor chip to which the present invention is applied, a plurality of the semiconductor elements in which the above-mentioned adhesive tape for dicing is sealed with a sealing resin made of a silicone resin are mounted on a substrate. A sticking step of sticking the semiconductor element substrate formed in the above from the sealing resin side, and a cutting step of cutting the semiconductor device substrate to which the adhesive tape for dicing is stuck into a plurality of semiconductor chips. A method for manufacturing a semiconductor chip, which includes an irradiation step of irradiating the dicing adhesive tape of the semiconductor element substrate with light, and a peeling step of peeling the dicing adhesive tape from the plurality of semiconductor chips.
　本発明によれば、複数の半導体素子が被覆材に被覆された半導体材料に対して、光照射前の段階においては、良好な粘着力およびタック力を有するとともに、光照射後にダイシングにより個片化された半導体チップを剥離した場合に、半導体チップの良好なピックアップ性を有するとともに、半導体チップに対する糊残りが抑制されたダイシング用粘着テープ、およびこれを用いた半導体チップの製造方法を提供することができる。 According to the present invention, a semiconductor material in which a plurality of semiconductor elements are coated with a coating material has good adhesive force and tack force before light irradiation, and is individualized by dicing after light irradiation. It is possible to provide an adhesive tape for dicing, which has good pick-up property of the semiconductor chip when the semiconductor chip is peeled off and suppresses adhesive residue on the semiconductor chip, and a method for manufacturing the semiconductor chip using the adhesive tape. it can.
本実施の形態が適用されるダイシング用粘着テープの構成の一例を示した図である。It is a figure which showed an example of the structure of the adhesive tape for dicing to which this embodiment is applied. （ａ）～（ｅ）は、本実施の形態の粘着テープを使用した半導体チップの製造方法を示した図である。(A) to (e) are diagrams showing a method of manufacturing a semiconductor chip using the adhesive tape of the present embodiment. 粘着剤層におけるシリコーン系樹脂の架橋密度と、粘着テープ１の保持力試験の結果（落下時間）との関係を示した模式図である。It is a schematic diagram which showed the relationship between the crosslink density of the silicone resin in the pressure-sensitive adhesive layer, and the result (drop time) of the holding force test of the pressure-sensitive adhesive tape 1.
　以下、添付図面を参照して本発明の実施の形態について詳細に説明する。
［粘着テープの構成］
　図１は、本実施の形態が適用されるダイシング用粘着テープ１（以下、単に粘着テープ１と称する）の構成の一例を示した図である。本実施の形態の粘着テープ１は、例えば、ＬＥＤ（Light Emitting Diode）やパワー半導体等の半導体素子を有する半導体チップの製造工程において、半導体チップの元となる半導体材料のダイシングに用いられる。 Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
[Structure of adhesive tape]
FIG. 1 is a diagram showing an example of a configuration of a dicing adhesive tape 1 (hereinafter, simply referred to as an adhesive tape 1) to which the present embodiment is applied. The adhesive tape 1 of the present embodiment is used for dicing a semiconductor material that is a source of a semiconductor chip in a process of manufacturing a semiconductor chip having a semiconductor element such as an LED (Light Emitting Diode) or a power semiconductor.
　図１に示すように、粘着テープ１は、基材２上に、粘着剤層３が積層された構成を有している。
　なお、図示は省略するが、粘着テープ１は、基材２と粘着剤層３との間に必要に応じて、基材２と粘着剤層３との密着性を高めるためのアンカーコート層を備えていてもよい。また、基材２の表面（粘着剤層３に対向する面とは反対側の面）に、表面処理が施されていてもよい。さらに、粘着剤層３の表面（基材２に対向する面とは反対側の面）に、剥離ライナーを備えていてもよい。 As shown in FIG. 1, the adhesive tape 1 has a structure in which the pressure-sensitive adhesive layer 3 is laminated on the base material 2.
Although not shown, the adhesive tape 1 has an anchor coat layer between the base material 2 and the pressure-sensitive adhesive layer 3 to improve the adhesion between the base material 2 and the pressure-sensitive adhesive layer 3, if necessary. You may have it. Further, the surface of the base material 2 (the surface opposite to the surface facing the pressure-sensitive adhesive layer 3) may be surface-treated. Further, a release liner may be provided on the surface of the pressure-sensitive adhesive layer 3 (the surface opposite to the surface facing the base material 2).
＜基材＞
　本実施の形態の基材２は、紫外線等の光を透過する材料により構成される。基材２の材料としては、紫外線等の光が透過可能であれば特に限定されるものではなく、例えば紫外線等の光が透過可能なプラスチック等を用いることができる。なお、ここで、紫外線等の光が透過可能とは、紫外線等の光の透過率が１００％であることを意味するものではなく、少なくとも粘着剤層３に含まれる後述する光感応白金（Ｐｔ）触媒によりシリコーン系樹脂と架橋剤との付加反応を促進できる程度の光が透過できればよい。 <Base material>
The base material 2 of the present embodiment is made of a material that transmits light such as ultraviolet rays. The material of the base material 2 is not particularly limited as long as it can transmit light such as ultraviolet rays, and for example, a plastic or the like that can transmit light such as ultraviolet rays can be used. Here, the fact that light such as ultraviolet rays can be transmitted does not mean that the transmittance of light such as ultraviolet rays is 100%, and at least the light-sensitive platinum (Pt) contained in the pressure-sensitive adhesive layer 3 will be described later. ) It is sufficient that the catalyst can transmit light to the extent that the addition reaction between the silicone resin and the cross-linking agent can be promoted.
　基材２の材料として具体的には、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリフェニレンサルファイド、二軸延伸ポリプロピレン、脂肪族ポリイミド（透明性ポリイミド）、ポリシクロオレフィン、フッ素系樹脂、ポリオレフィン樹脂等の樹脂フィルムを用いることができる。また、用途に応じて基材２には、例えば、ポリエチレンテレフタレートとポリオレフィン樹脂フィルムとをラミネートした複合フィルム、およびこれらの複合フィルムをさらに樹脂フィルムとラミネートした複合フィルム、共押し出しで複層とした樹脂フィルム等を用いてもよい。
　この中でも、基材２としては、ポリエチレンテレフタレートを主成分とする材料を用いることが好ましい。 Specifically, as the material of the base material 2, resin films such as polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, biaxially stretched polypropylene, aliphatic polyimide (transparent polyimide), polycycloolefin, fluororesin, and polyolefin resin are used. Can be used. Further, depending on the application, the base material 2 includes, for example, a composite film obtained by laminating polyethylene terephthalate and a polyolefin resin film, a composite film obtained by further laminating these composite films with a resin film, and a resin formed into a multi-layer by coextrusion. A film or the like may be used.
Among these, as the base material 2, it is preferable to use a material containing polyethylene terephthalate as a main component.
＜粘着剤層＞
　本実施の形態の粘着剤層３は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが混合されたシリコーン系樹脂、１分子中に少なくとも２個以上のケイ素原子結合水素原子（ＳｉＨ基）を有するシリコーン系樹脂に対する架橋剤、熱重合開始剤として過酸化物および、光感応白金（Ｐｔ）触媒を含む粘着剤組成物により構成される。
　シリコーン系樹脂は、「ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）を含むシリコーンガム（Ｇ）」と、「オルガノポリシロキサンからなるシリコーンレジン（Ｒ）」とが所定の比率で配合された混合樹脂からなる。以下、粘着剤層３を構成する粘着剤組成物に含まれる各成分について順に説明する。 <Adhesive layer>
The pressure-sensitive adhesive layer 3 of the present embodiment contains at least two or more silicon atom-bonded hydrogen atoms (SiH groups) in one molecule of a silicone-based resin in which silicone gum (G) and silicone resin (R) are mixed. It is composed of a pressure-sensitive adhesive composition containing a cross-linking agent for a silicone-based resin, a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst.
The silicone-based resin is defined as "a silicone gum (G ) containing a silicone gum (G alk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group" and "a silicone resin (R) made of an organopolysiloxane". It consists of a mixed resin blended in the ratio of. Hereinafter, each component contained in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 will be described in order.
（シリコーン系樹脂）
　本実施の形態のシリコーン系樹脂は、「ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）を含むシリコーンガム（Ｇ）」と、「オルガノポリシロキサンからなるシリコーンレジン（Ｒ）」とが、４０．０／６０．０～５６．０／４４．０の範囲となるように配合された混合樹脂からなる。すなわち、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が、質量比で４０．０／６０．０～５６．０／４４．０の範囲となるように配合された混合樹脂からなる。
　また、シリコーン系樹脂は、シリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量が７．０×１０-7ｍｏｌ／ｇ以上５．５×１０-6ｍｏｌ／ｇ以下の範囲となるように構成され、より好ましくは、２．９×１０-6ｍｏｌ／ｇ以上４．１×１０-5ｍｏｌ／ｇ以下の範囲となるように構成される。ここで「ｍｏｌ／ｇ」は、「シリコーン系樹脂全体の固形分１ｇあたりの物質量」を意味する。 (Silicone resin)
The silicone-based resin of the present embodiment includes "silicone gum (G) containing silicone gum (G alk ) made of organopolysiloxane containing a silicon atom-bonded alkenyl group" and "silicone resin (R) made of organopolysiloxane". ) ”Is composed of a mixed resin blended so as to be in the range of 40.0 / 60.0 to 56.0 / 44.0. That is, the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) is in the range of 40.0 / 60.0 to 56.0 / 44.0 in terms of mass ratio. It consists of a mixed resin formulated as described above.
Further, the silicone-based resin is configured such that the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 7.0 × 10 -7 mol / g or more and 5.5 × 10 -6 mol / g or less. It is more preferably configured so as to have a range of 2.9 × 10 -6 mol / g or more and 4.1 × 10 -5 mol / g or less. Here, "mol / g" means "amount of substance per 1 g of solid content of the entire silicone-based resin".
　シリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量が７．０×１０-7ｍｏｌ／ｇ未満であると、粘着テープ１に紫外線等の光を照射した際に、シリコーンガムが有するケイ素原子結合アルケニル基と架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間の２段階目の架橋反応（付加反応）による架橋密度の向上が不十分となり、粘着剤が硬化し難く、凝集力が向上しにくくなる。この場合、所望のタック力低下や保持力試験における破壊モードが得られず、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際に、個片化された半導体チップのピックアップ性が悪くなるおそれや、半導体チップ等に糊残りが生じやすくなるおそれがある。
　一方、シリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量が５．５×１０-6ｍｏｌ／ｇを超えると、粘着剤層３を構成する粘着剤組成物のシリコーン系樹脂においてシリコーンガム（Ｇ）の混合比率が高い場合に、熱重合開始剤の種類や含有量によっては、紫外線等の光照射前の段階で、シリコーン系樹脂の硬化（１段階目の架橋反応）が熱重合開始剤により進み過ぎて、粘着剤層３が硬くなり過ぎる場合がある。この場合、粘着テープ１を半導体素子基板等のダイシングに使用すると、半導体素子基板等を切断する際に、切断片である半導体チップ等が粘着テープ１から剥がれて飛散しやすくなるおそれがある。 When the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is less than 7.0 × 10 -7 mol / g, the silicon atom bond possessed by the silicone gum when the adhesive tape 1 is irradiated with light such as ultraviolet rays. The improvement of the cross-linking density by the second-stage cross-linking reaction (addition reaction) between the alkenyl group and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent becomes insufficient, the adhesive is hard to cure, and the cohesive force is increased. It becomes difficult to improve. In this case, the desired reduction in tack force and the breaking mode in the holding force test cannot be obtained, and after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1. , There is a risk that the pickability of the individualized semiconductor chip will deteriorate, and there is a risk that adhesive residue will easily occur on the semiconductor chip or the like.
On the other hand, when the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin exceeds 5.5 × 10 -6 mol / g, the silicone-based resin of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 contains silicone gum (G). ), Depending on the type and content of the thermal polymerization initiator, the silicone-based resin may be cured (first-step cross-linking reaction) by the thermal polymerization initiator before irradiation with light such as ultraviolet rays. The pressure-sensitive adhesive layer 3 may become too hard due to excessive progress. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
　シリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量は、シリコーン系樹脂の不揮発成分に対して、1Ｈ－ＮＭＲ（核磁気共鳴）スペクトル測定を行い、アルケニル基の共鳴シグナル面積（積分値）を求めることにより算出することができる。詳細は後述する。 For the content of silicon atom-bonded alkenyl groups in the entire silicone-based resin, 1 H-NMR (nuclear magnetic resonance) spectrum measurement was performed on the non-volatile components of the silicone-based resin, and the resonance signal area (integrated value) of the alkenyl groups was determined. It can be calculated by obtaining it. Details will be described later.
　なお、本実施の形態のシリコーン系樹脂は、「シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））」および「ケイ素原子結合アルケニル基の含有量」が上記の範囲であれば、ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンから成るシリコーンガム（Ｇ0）を含んでいてもよい。すなわち、シリコーンガム（Ｇ）は、「ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）」の単独物あるいはそれらの２種以上の混合物であってもよいし、「ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）」と「ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンからなるシリコーンガム（Ｇ0）」の混合物あるいはそれらの２種以上の混合物であってもよい。 The silicone-based resin of the present embodiment has "mixing ratio of silicone gum (G) and silicone resin (R) ((G) / (R))" and "content of silicon atom-bonded alkenyl group". Within the above range, a silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group may be contained. That is, the silicone gum (G) may be a single substance of "silicone gum (G alk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group" or a mixture of two or more thereof, or "silicon". A mixture of "silicone gum (G alk ) made of organopolysiloxane containing an atomic bond alkenyl group " and "silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atomic bond alkenyl group" or two or more of them. It may be a mixture.
　以下、シリコーン系樹脂に含まれる、「ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンから成るシリコーンガム（Ｇalk）」、「ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンから成るシリコーンガム（Ｇ0）」と、「ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンから成るシリコーンレジン（Ｒ）」についてさらに詳しく説明する。
　なお、以下の説明において、ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンから成るシリコーンガム（Ｇalk）を、ケイ素原子結合アルケニル基を含有するシリコーンガム（Ｇalk）、または、単にシリコーンガム（Ｇalk）と表記する場合がある。同様に、ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンから成るシリコーンガム（Ｇ0）を、ケイ素原子結合アルケニル基を含有しないシリコーンガム（Ｇ0）、または、単にシリコーンガム（Ｇ0）と表記する場合がある。さらに、オルガノポリシロキサンから成るシリコーンレジン（Ｒ）を、単にシリコーンレジン（Ｒ）と表記する場合がある。 Hereinafter, "silicone gum composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group (G alk )" and "silicone gum composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group (G 0)" contained in a silicone-based resin ) ”And“ Silicone resin (R) composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group ”will be described in more detail.
In the following description, the silicone gum (G alk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group is referred to as a silicone gum (G alk ) containing a silicon atom-bonded alkenyl group, or simply a silicone gum (G). It may be written as alk). Similarly, a silicone gum (G 0 ) composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group is referred to as a silicone gum (G 0 ) containing no silicon atom-bonded alkenyl group, or simply a silicone gum (G 0 ). May be done. Further, the silicone resin (R) composed of organopolysiloxane may be simply referred to as silicone resin (R).
（ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk））
　本実施の形態におけるケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）は、一般的に付加反応型シリコーン系樹脂として使用されるもの、すなわち、平均して１分子中に少なくとも２個のケイ素原子結合アルケニル基を含有するものであればよく、特に限定されるものではない。
　具体的には、シリコーンガム（Ｇalk）としては、ケイ素原子結合アルケニル基の含有量が１．０×１０-6ｍｏｌ／ｇ以上１．０×１０-1ｍｏｌ／ｇ以下の範囲であるものを使用することができる。本実施の形態では、粘着剤層３の粘着特性の制御、あるいは市販品を使用する場合の入手のし易さの観点から、ケイ素原子結合アルケニル基の含有量が１．７×１０-6ｍｏｌ／ｇ以上１．０×１０-2ｍｏｌ／ｇ以下の範囲であるものを使用することが好ましい。このシリコーンガム（Ｇalk）は、上述したシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが混合されたシリコーン系樹脂全体におけるアルケニル基の含有量が７．０×１０-7ｍｏｌ／ｇ以上５．５×１０-6ｍｏｌ／ｇ以下の範囲となるように、１種を単独で用いてもよいし、２種以上を併用してもよい。 (Silicone gum (G alk ) composed of organopolysiloxane containing a silicon atom-bonded alkenyl group)
The silicone gum (Galk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group in the present embodiment is generally used as an addition reaction type silicone resin, that is, in one molecule on average. It is not particularly limited as long as it contains at least two silicon atom-bonded alkenyl groups.
Specifically, as the silicone gum (G alk), those content of silicon-bonded alkenyl groups is in the range below 1.0 × 10 -6 mol / g or more 1.0 × 10 -1 mol / g Can be used. In the present embodiment, the content of the silicon atom-bonded alkenyl group is 1.7 × 10 -6 mol from the viewpoint of controlling the adhesive properties of the pressure-sensitive adhesive layer 3 or making it easily available when a commercially available product is used. It is preferable to use one having a range of / g or more and 1.0 × 10 −2 mol / g or less. This silicone gum (G alk ) has an alkenyl group content of 7.0 × 10 -7 mol / g or more in the entire silicone-based resin in which the above-mentioned silicone gum (G) and silicone resin (R) are mixed 5 One type may be used alone or two or more types may be used in combination so as to have a range of .5 × 10 -6 mol / g or less.
　シリコーンガム（Ｇalk）を構成するケイ素原子結合アルケニル基を含有するオルガノポリシロキサンの分子構造としては、例えば、主鎖部分がジオルガノシロキサン単位の繰り返しからなる直鎖状構造、当該分子構造の一部に分枝鎖を含んだ構造、分岐鎖状構造、または環状体構造が挙げられる。中でも、紫外線等の光の照射後の粘着剤の機械的強度および物性等の点から、直鎖状構造のオルガノポリシロキサンが好ましい。 The molecular structure of the organopolysiloxane containing the silicon atom-bonded alkenyl group constituting the silicone gum ( Galk ) is, for example, a linear structure in which the main chain portion is a repetition of diorganosiloxane units, and one of the molecular structures. Examples thereof include a structure containing a branched chain, a branched chain structure, and an annular structure. Of these, an organopolysiloxane having a linear structure is preferable from the viewpoint of mechanical strength and physical properties of the pressure-sensitive adhesive after irradiation with light such as ultraviolet rays.
　ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）は、オイル状又は生ゴム状のいずれであってもよいが、生ゴム状であることが好ましい。オイル状である場合、オルガノポリシロキサンからなるシリコーンガム（Ｇalk）の粘度は、２５℃において、１，０００ｍＰａ・ｓ以上が好ましい。粘度が１，０００ｍＰａ・ｓ未満では、紫外線等の光照射前後の粘着剤が所望の粘着特性を発現できないおそれや、粘着剤層３と基材２との密着性が劣るおそれがある。生ゴム状である場合、オルガノポリシロキサンからなるシリコーンガム（Ｇalk）を３０質量％の濃度となるようにトルエンで溶解した場合の粘度は、２５℃において１００，０００ｍＰａ・ｓ以下が好ましい。粘度が１００，０００ｍＰａ・ｓを超えると、粘着剤組成物を調製する際の撹拌が困難になるおそれがある。なお、オルガノポリシロキサンからなるシリコーンガム（Ｇalk）の粘度はＢ型回転粘度計（ＢＭ形ローター使用、以下同じ）を用いて測定することができる。 The silicone gum (Galk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group may be in the form of oil or raw rubber, but is preferably in the form of raw rubber. If it is oily, viscosity of the silicone gum (G alk) consisting of organopolysiloxane at 25 ° C., or higher 1,000 mPa · s is preferable. If the viscosity is less than 1,000 mPa · s, the pressure-sensitive adhesive before and after irradiation with light such as ultraviolet rays may not exhibit the desired pressure-sensitive adhesive properties, or the adhesion between the pressure-sensitive adhesive layer 3 and the base material 2 may be inferior. In the case of raw rubber, the viscosity of silicone gum ( Galk ) made of organopolysiloxane when dissolved in toluene so as to have a concentration of 30% by mass is preferably 100,000 mPa · s or less at 25 ° C. If the viscosity exceeds 100,000 mPa · s, it may be difficult to stir when preparing the pressure-sensitive adhesive composition. The viscosity of the silicone gum ( Galk ) made of organopolysiloxane can be measured using a B-type rotational viscometer (using a BM type rotor, the same applies hereinafter).
　ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）は、例えば、下記一般式（１）または一般式（２）で示すものが挙げられるが、これらに限定されるものではない。 Examples of the silicone gum (Galk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group include those represented by the following general formula (1) or general formula (2), but are not limited thereto. Absent.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ここで、上記一般式（１）、一般式（２）において、Ｒ1は、互いに独立に、脂肪族不飽和結合を有さない１価炭化水素基であり、Ｘはアルケニル基含有有機基である。ａは０～３の整数であり、ｍは０以上の整数であり、ｎは１００以上の整数であり、但しａとｍは同時に０にならず、ａが０の場合に限り、ｍは２以上の整数である。ｍ＋ｎは、上記オルガノポリシロキサンからなるシリコーンガム（Ｇalk）の２５℃における粘度が１，０００ｍＰａ・ｓ以上となる値である。 Here, in the general formulas (1) and (2), R 1 is a monovalent hydrocarbon group independently of each other and does not have an aliphatic unsaturated bond, and X is an alkenyl group-containing organic group. is there. a is an integer of 0 to 3, m is an integer of 0 or more, n is an integer of 100 or more, where a and m do not become 0 at the same time, and m is 2 only when a is 0. It is the above integer. m + n is a value at which the viscosity becomes 1,000 mPa · s or higher at 25 ° C. of the silicone gum (G alk) consisting of the organopolysiloxane.
　Ｒ1としては、炭素数１～１０、好ましくは炭素数１～７の、脂肪族不飽和結合を有さない１価炭化水素基が好ましい。例えば、メチル基、エチル基、プロピル基、及びブチル基などのアルキル基；シクロヘキシル基等のシクロアルキル基；及びフェニル基、及びトリル基等のアリール基等が挙げられ、特に、メチル基又はフェニル基が好ましい。 As R 1 , a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms and having no aliphatic unsaturated bond is preferable. Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl group such as cyclohexyl group; and aryl group such as phenyl group and tolyl group, and in particular, methyl group or phenyl group. Is preferable.
　Ｘとしては、炭素数２～１０のアルケニル基含有有機基が好ましい。例えば、ビニル基、アリル基、ヘキセニル基、オクテニル基、アクリロイルプロピル基、アクリロイルメチル基、メタクリロイルプロピル基、アクリロキシプロピル基、アクリロキシメチル基、メタクリロキシプロピル基、メタクリロキシメチル基、シクロヘキセニルエチル基、及びビニルオキシプロピル基等が挙げられる。中でも、ビニル基、アリル基等の低級アルケニル基が好ましく、工業的観点から、特にはビニル基が好ましい。アルケニル基の結合位置は特に限定されず、分子鎖末端、分子鎖側鎖又は分子鎖末端と分子鎖側鎖両方でもよい。 As X, an alkenyl group-containing organic group having 2 to 10 carbon atoms is preferable. For example, vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, acryloxypropyl group, acryloxymethyl group, methaloxypropyl group, methaloxymethyl group, cyclohexenylethyl group. , And vinyloxypropyl group and the like. Among them, a lower alkenyl group such as a vinyl group and an allyl group is preferable, and a vinyl group is particularly preferable from an industrial point of view. The bonding position of the alkenyl group is not particularly limited, and may be a molecular chain end, a molecular chain side chain, or both a molecular chain end and a molecular chain side chain.
　アルケニル基の数は、シリコーン系粘着剤に含まれるオルガノポリシロキサンからなるシリコーンレジン（Ｒ）の含有量、架橋剤の種類・添加量、他の添加成分との兼ね合い等により適切な範囲が変わるので、一概には言えないが、例えば、オルガノポリシロキサンのオルガノ基１００個に対して、通常０．１個以上３．０個以下の範囲であることが好ましい。そして、この比率の範囲で、上述した粘度の範囲となるように分子量を調整して、平均してオルガノポリシロキサン１分子中の上記アルケニル基の数が少なくとも２個となるように調整することが好ましい。アルケニル基の数がオルガノポリシロキサンのオルガノ基１００個に対して０．１個未満であると、粘着テープ１に紫外線等の光を照射した際に、シリコーンガム（Ｇalk）が有するケイ素原子結合アルケニル基とシリコーン系樹脂に対する架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間の２段階目の架橋反応（付加反応）による架橋密度の向上が不十分となり、粘着剤が硬化し難く、凝集力が向上しにくくなる。この場合、所望のタック力低下や保持力試験における破壊モードが得られず、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際に、個片化された半導体チップのピックアップ性が悪くなるおそれや、半導体チップ等に糊残りが生じやすくなるおそれがある。一方、アルケニル基の数がオルガノポリシロキサンのオルガノ基１００個に対して３．０個を超えると、粘着剤層３を構成する粘着剤組成物のシリコーン系樹脂においてシリコーンガム（Ｇ）の混合比率が高い場合に、熱重合開始剤の種類や含有量によっては、紫外線等の光照射前の段階で、シリコーン系樹脂の硬化（１段階目の架橋反応）が熱重合開始剤により進み過ぎて、粘着剤層３が硬くなり過ぎる場合がある。この場合、粘着テープ１を半導体素子基板等のダイシングに使用すると、半導体素子基板等を切断する際に、切断片である半導体チップ等が粘着テープ１から剥がれて飛散しやすくなるおそれがある。 The appropriate range of the number of alkenyl groups varies depending on the content of the silicone resin (R) composed of organopolysiloxane contained in the silicone-based pressure-sensitive adhesive, the type and amount of the cross-linking agent, and the balance with other additive components. Although it cannot be said unconditionally, for example, it is preferably in the range of 0.1 or more and 3.0 or less with respect to 100 organogroups of the organopolysiloxane. Then, within this ratio range, the molecular weight may be adjusted so as to be within the above-mentioned viscosity range so that the number of the alkenyl groups in one molecule of organopolysiloxane is at least 2 on average. preferable. When the number of alkenyl groups is less than 0.1 with respect to 100 organogroups of the organopolysiloxane, the silicon atom bond possessed by the silicone gum (Galk) when the adhesive tape 1 is irradiated with light such as ultraviolet rays. The improvement of the cross-linking density by the second-step cross-linking reaction (addition reaction) between the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent for the alkenyl group and the silicone-based resin becomes insufficient, and the adhesive is difficult to cure. , It becomes difficult to improve the cohesive force. In this case, the desired reduction in tack force and the breaking mode in the holding force test cannot be obtained, and after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1. , There is a risk that the pickability of the individualized semiconductor chip will deteriorate, and there is a risk that adhesive residue will easily occur on the semiconductor chip or the like. On the other hand, when the number of alkenyl groups exceeds 3.0 with respect to 100 organopolysiloxanes, the mixing ratio of the silicone gum (G) in the silicone-based resin of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 If the value is high, depending on the type and content of the thermal polymerization initiator, the curing of the silicone-based resin (first-step cross-linking reaction) may proceed too much due to the thermal polymerization initiator before irradiation with light such as ultraviolet rays. The pressure-sensitive adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
　このようなケイ素原子結合アルケニル基を含有するシリコーンガム（Ｇalk）の具体例としては、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルフェニルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルヘキセニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルヘキセニルシロキサン共重合体、分子鎖両末端ジメチルヘキセニルシロキシ基封鎖ジメチルシロキサン・メチルヘキセニルシロキサン共重合体等が挙げられる。 Specific examples of silicone gums containing such silicon-bonded alkenyl groups (G alk), dimethylpolysiloxane with both molecular chain terminals blocked with dimethylvinylsiloxy groups at both molecular chain terminals with dimethylvinylsiloxy groups dimethylsiloxane-methylvinyl Siloxane copolymer, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain, dimethylvinylsiloxy group-blocked methylphenylpolysiloxane at both ends of the molecular chain, trimethylsiloxy group-blocked dimethylsiloxane / methyl at both ends of the molecular chain Vinylsiloxane copolymer, trimethylsiloxy group-blocking at both ends of the molecular chain dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-blocking at both ends of the molecular chain dimethylsiloxane / methylhexenylsiloxane copolymer, both ends of the molecular chain Examples thereof include a dimethylvinylsiloxy group-blocking dimethylsiloxane / methylhexenylsiloxane copolymer and a dimethylhexenylsiloxy group-blocking dimethylsiloxane / methylhexenylsiloxane copolymer at both ends of the molecular chain.
（ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンからなるシリコーンガム（Ｇ0））
　本実施の形態におけるケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンからなるシリコーンガム（Ｇ0）は、一般的に過酸化物硬化型シリコーン系樹脂として使用されるもの、すなわち、ケイ素原子結合アルケニル基を含有していないものであればよく、特に限定されるものではない。
　このようなシリコーンガム（Ｇ0）を構成するオルガノポリシロキサンの分子構造としては、例えば、主鎖部分がジオルガノシロキサン単位の繰り返しからなる直鎖状構造、該分子構造の一部に分枝鎖を含んだ構造、分岐鎖状構造、または環状体構造が挙げられる。 (Silicone gum (G 0 ) made of organopolysiloxane containing no silicon atom-bonded alkenyl group)
The silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group in the present embodiment is generally used as a peroxide-curable silicone-based resin, that is, a silicon atom-bonded alkenyl group. It is not particularly limited as long as it does not contain.
The molecular structure of the organopolysiloxane constituting such a silicone gum (G 0 ) is, for example, a linear structure in which the main chain portion is a repetition of diorganosiloxane units, and a branched chain in a part of the molecular structure. Examples thereof include a structure containing a siloxane, a branched chain structure, or an annular structure.
　ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンからなるシリコーンガム（Ｇ0）は、オイル状又は生ゴム状のいずれであってもよいが、生ゴム状であることが好ましい。オイル状である場合、オルガノポリシロキサンからなるシリコーンガム（Ｇ0）の粘度は、２５℃において、１，０００ｍＰａ・ｓ以上が好ましい。粘度が１，０００ｍＰａ・ｓ未満では、紫外線等の光照射前後の粘着剤が所望の粘着特性を発現できないおそれや、粘着剤層３と基材２との密着性が劣るおそれがある。生ゴム状である場合、オルガノポリシロキサンからなるシリコーンガム（Ｇ0）を３０質量％の濃度となるようにトルエンで溶解した時の粘度は、２５℃において１００，０００ｍＰａ・ｓ以下が好ましい。粘度が１００，０００ｍＰａ・ｓを超えると、粘着剤組成物を調製する際の撹拌が困難になるおそれがある。なお、オルガノポリシロキサンからなるシリコーンガム（Ｇ0）の粘度はＢ型回転粘度計を用いて測定することができる。 The silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group may be in the form of oil or raw rubber, but is preferably in the form of raw rubber. When in the form of oil, the viscosity of the silicone gum (G 0 ) made of organopolysiloxane is preferably 1,000 mPa · s or more at 25 ° C. If the viscosity is less than 1,000 mPa · s, the pressure-sensitive adhesive before and after irradiation with light such as ultraviolet rays may not exhibit the desired pressure-sensitive adhesive properties, or the adhesion between the pressure-sensitive adhesive layer 3 and the base material 2 may be inferior. In the case of a raw rubber, the viscosity of silicone gum (G 0 ) made of organopolysiloxane when dissolved in toluene so as to have a concentration of 30% by mass is preferably 100,000 mPa · s or less at 25 ° C. If the viscosity exceeds 100,000 mPa · s, it may be difficult to stir when preparing the pressure-sensitive adhesive composition. The viscosity of the silicone gum (G 0 ) made of organopolysiloxane can be measured using a B-type rotational viscometer.
　ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンからなるシリコーンガム（Ｇ0）は、例えば、下記一般式（３）または一般式（４）で示すものが挙げられるが、これらに限定されるものではない。 Examples of the silicone gum (G 0 ) made of an organopolysiloxane containing no silicon atom-bonded alkenyl group include those represented by the following general formula (3) or general formula (4), but are not limited thereto. Absent.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　ここで、上記一般式（３）、一般式（４）において、Ｒ4は、互いに独立に、脂肪族不飽和結合を有さない１価炭化水素基であり、ｔは、１００以上の整数で、上記ジオルガノポリシロキサンからなるシリコーンガム（Ｇ0）の２５℃における粘度が１，０００ｍＰａ・ｓ以上となる値である。 Here, in the above general formulas (3) and (4), R 4 is a monovalent hydrocarbon group which is independent of each other and does not have an aliphatic unsaturated bond, and t is an integer of 100 or more. , The viscosity of the silicone gum (G 0 ) made of the above diorganopolysiloxane at 25 ° C. is a value of 1,000 mPa · s or more.
　Ｒ4としては、炭素数１～１０、好ましくは炭素数１～７の、脂肪族不飽和結合を有さない１価炭化水素基が好ましい。例えば、メチル基、エチル基、プロピル基、及びブチル基などのアルキル基；シクロヘキシル基等のシクロアルキル基；及びフェニル基、及びトリル基等のアリール基等が挙げられ、特に、メチル基が好ましい。 As R 4 , a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms and having no aliphatic unsaturated bond is preferable. Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl group such as cyclohexyl group; and aryl group such as phenyl group and tolyl group, and methyl group is particularly preferable.
（オルガノポリシロキサンからなるシリコーンレジン（Ｒ））
　本実施の形態におけるオルガノポリシロキサンからなるシリコーンレジン（Ｒ）は、Ｒ2 3ＳｉＯ0.5単位（Ｍ単位）およびＳｉＯ2単位（Ｑ単位）を有するオルガノポリシロキサンであり、一般的にシリコーン系粘着剤に使用される所謂ＭＱレジンと称されるものである。このオルガノポリシロキサンからなるシリコーンレジン（Ｒ）は、基本的には分子内にアルケニル基を有しておらず、従来公知のものを使用することができる。Ｒ2は炭素数１～１０の１価炭化水素基であり、上述のＲ1として例示したものが挙げられる。シリコーンレジン（Ｒ）を構成するオルガノポリシロキサンは、Ｒ2 3ＳｉＯ0.5単位およびＳｉＯ2単位を、Ｒ2 3ＳｉＯ0.5単位／ＳｉＯ2単位のモル比で０．５以上１．７以下の範囲となるように含有することが好ましい。Ｒ2 3ＳｉＯ0.5単位／ＳｉＯ2単位のモル比が０．５未満では、得られる粘着剤層３の粘着力やタック力が低下する場合がある。一方、Ｒ2 3ＳｉＯ0.5単位／ＳｉＯ2単位のモル比が１．７を超えると、得られる粘着剤層３の粘着力や保持力が低下する場合がある。なお、シリコーンレジン（Ｒ）を構成するオルガノポリシロキサンはＯＨ基を有していてもよい。その場合、ＯＨ基の含有量は、オルガノポリシロキサンの総質量に対して４．０質量％以下であるのが好ましい。ＯＨ基の含有量が４．０質量％を超えると、粘着剤の硬化性が低下するおそれがある。 (Silicone resin (R) composed of organopolysiloxane)
The silicone resin (R) composed of the organopolysiloxane in the present embodiment is an organopolysiloxane having R 2 3 SiO 0.5 unit (M unit) and SiO 2 unit (Q unit), and is generally a silicone-based pressure-sensitive adhesive. It is a so-called MQ resin used in the above. The silicone resin (R) composed of this organopolysiloxane basically does not have an alkenyl group in the molecule, and conventionally known ones can be used. R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include those exemplified as R 1 described above. The organopolysiloxane constituting the silicone resin (R) has R 2 3 SiO 0.5 units and SiO 2 units in the range of 0.5 or more and 1.7 or less in a molar ratio of R 2 3 SiO 0.5 units / SiO 2 units. It is preferable to contain it so as to become. If the molar ratio of R 2 3 SiO 0.5 unit / SiO 2 unit is less than 0.5, the adhesive strength and tack strength of the obtained pressure-sensitive adhesive layer 3 may decrease. On the other hand, if the molar ratio of R 2 3 SiO 0.5 unit / SiO 2 unit exceeds 1.7, the adhesive strength and holding power of the obtained pressure-sensitive adhesive layer 3 may decrease. The organopolysiloxane constituting the silicone resin (R) may have an OH group. In that case, the content of the OH group is preferably 4.0% by mass or less with respect to the total mass of the organopolysiloxane. If the content of OH groups exceeds 4.0% by mass, the curability of the pressure-sensitive adhesive may decrease.
　上記オルガノポリシロキサンは２種以上を併用してもよい。また、上記オルガノポリシロキサンは、本発明の特性を損なわない範囲で、Ｒ2ＳｉＯ1.5単位（Ｔ単位）及び／又はＲ2 2ＳｉＯ単位（Ｄ単位）を有していてもよい。 Two or more kinds of the above-mentioned organopolysiloxane may be used in combination. Further, the organopolysiloxane may have R 2 SiO 1.5 units (T units) and / or R 2 2 SiO units (D units) as long as the characteristics of the present invention are not impaired.
　「ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）」と「ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンからなるシリコーンガム（Ｇ0）」と「オルガノポリシロキサンからなるシリコーンレジン（Ｒ）」とは、通常は単純に混合して使用すればよい。また、ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）として、上記一般式（２）で示されるオルガノポリシロキサンを含有する場合や、ケイ素原子結合アルケニル基を含有しないオルガノポリシロキサンからなるシリコーンガム（Ｇ0）として、上記一般式（４）で示されるオルガノポリシロキサンを含有する場合には、本発明の特性を損なわない限りにおいては、シリコーンガム（Ｇalk）とシリコーンレジン（Ｒ）とを、あるいはシリコーンガム（Ｇ0）とシリコーンレジン（Ｒ）とを、予め反応させて得られる（部分）縮合反応物として使用してもよい。 "Silicone gum (G alk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group ", "Silicone gum (G 0 ) composed of an organopolysiloxane containing no silicon atom-bonded alkenyl group", and "Consists of an organopolysiloxane" The "silicone resin (R)" may usually be simply mixed and used. Further, as a silicone gum ( Galk ) composed of an organopolysiloxane containing a silicon atom-bonded alkenyl group, a case where the organopolysiloxane represented by the above general formula (2) is contained, or an organo without a silicon atom-bonded alkenyl group is contained. When the silicone gum (G 0 ) composed of polysiloxane contains the organopolysiloxane represented by the above general formula (4), the silicone gum (G alk ) and silicone are provided as long as the characteristics of the present invention are not impaired. The resin (R) or the silicone gum (G 0 ) and the silicone resin (R) may be reacted in advance to be used as a (partial) condensation reaction product.
（シリコーン系樹脂全体におけるシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ）））
　本実施形態の粘着剤層３に含まれるシリコーン系樹脂全体において、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））は、質量比で４０．０／６０．０～５６．０／４４．０の範囲である。ここで、シリコーンガム（Ｇ）を２種以上併用する場合は、それぞれのシリコーンガム（Ｇ）の合計量を、シリコーン系樹脂全体におけるシリコーンガム（Ｇ）の質量と見做す。例えば、シリコーンガム（Ｇ）として、シリコーンガム（Ｇalk）とシリコーンガム（Ｇ0）を併用した場合、シリコーン系樹脂全体におけるシリコーンガム（Ｇ）の質量は、シリコーンガム（Ｇalk）の質量とシリコーンガム（Ｇ0）の質量との合計量である。同様に、シリコーンレジン（Ｒ）を２種以上併用する場合も、それぞれのシリコーンレジンの合計量を、シリコーン系樹脂全体におけるシリコーンレジン（Ｒ）の質量と見做す。 (Mixing ratio of silicone gum (G) and silicone resin (R) in the entire silicone resin ((G) / (R)))
The mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) in the entire silicone-based resin contained in the pressure-sensitive adhesive layer 3 of the present embodiment is 40.0 / by mass ratio. It is in the range of 60.0 to 56.0 / 44.0. Here, when two or more types of silicone gum (G) are used in combination, the total amount of each silicone gum (G) is regarded as the mass of the silicone gum (G) in the entire silicone-based resin. For example, when silicone gum (G alk ) and silicone gum (G 0 ) are used in combination as the silicone gum (G), the mass of the silicone gum (G) in the entire silicone-based resin is the mass of the silicone gum (G alk ). It is the total amount with the mass of silicone gum (G 0). Similarly, when two or more types of silicone resins (R) are used in combination, the total amount of each silicone resin is regarded as the mass of the silicone resin (R) in the entire silicone resin.
　本実施形態の粘着剤層３に含まれるシリコーン系樹脂全体において、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が上記範囲の下限値未満であると、粘着テープ１に紫外線等の光を照射した際に、シリコーンガム（Ｇ）が有するケイ素原子結合アルケニル基とシリコーン系樹脂に対する架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間の２段階目の架橋反応（付加反応）による架橋密度の向上の寄与が不十分となり、粘着剤が硬化し難く、凝集力が向上しにくくなる。この場合、所望のタック力低下や保持力試験における破壊モードが得られず、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際に、個片化された半導体チップのピックアップ性が悪くなるおそれや、半導体チップ等に糊残りが生じやすくなるおそれがある。 In the entire silicone-based resin contained in the pressure-sensitive adhesive layer 3 of the present embodiment, the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) is less than the lower limit of the above range. And the silicon atom-bonded alkenyl group of the silicone gum (G) and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent for the silicone-based resin when the adhesive tape 1 is irradiated with light such as ultraviolet rays. The contribution of the improvement of the cross-linking density by the second-stage cross-linking reaction (addition reaction) becomes insufficient, the adhesive is hard to cure, and the cohesive force is hard to improve. In this case, the desired reduction in tack force and the breaking mode in the holding force test cannot be obtained, and after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1. , There is a risk that the pickability of the individualized semiconductor chip will deteriorate, and there is a risk that adhesive residue will easily occur on the semiconductor chip or the like.
　一方、本実施形態の粘着剤層３に含まれるシリコーン系樹脂全体において、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が上記範囲の上限値を超えると、紫外線等の光照射前の段階で、シリコーン系樹脂の硬化（１段階目の架橋反応）が熱重合開始剤により進み過ぎて、粘着剤層３が硬くなり過ぎる場合がある。この場合、粘着テープ１を半導体素子基板等のダイシングに使用すると、半導体素子基板等を切断する際に、切断片である半導体チップ等が粘着テープ１から剥がれて飛散しやすくなるおそれがある。 On the other hand, in the entire silicone-based resin contained in the pressure-sensitive adhesive layer 3 of the present embodiment, the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) has an upper limit value in the above range. If it exceeds the limit, the curing of the silicone-based resin (first-stage cross-linking reaction) may proceed too much due to the thermal polymerization initiator before irradiation with light such as ultraviolet rays, and the pressure-sensitive adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
　これに対し、本実施形態の粘着剤層３に含まれるシリコーン系樹脂全体において、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））を上述した４０．０／６０．０～５６．０／４４．０の範囲とすることにより、以下の効果を実現できる。すなわち、紫外線等の光の照射前の段階においては、粘着剤層３は、熱重合開始剤によりシリコーン系樹脂の一部が架橋・硬化（１段階目の架橋反応）された状態になっているため、粘着剤層３に対して、ダイシングの際に切断片である半導体チップ等の飛散が発生しない適切な粘着力およびタック力を付与させることが可能となる。一方、紫外線等の光の照射後は、粘着剤層３のシリコーン系樹脂は、上述したようにシリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量が７．０×１０-7ｍｏｌ／ｇ以上５．５×１０-6ｍｏｌ／ｇ以下の範囲となるように構成されているので、シリコーンガム（Ｇ）が有するケイ素原子結合アルケニル基とシリコーン系樹脂に対する架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間で２段階目の架橋反応（付加反応）が十分に進む。これにより、粘着剤層３の硬化がさらに進行することで、架橋密度が高くなり、凝集力がさらに向上するため、所望のタック力の低下や保持力試験における破壊モードが得られるようになる。この結果、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際の良好なピックアップ性を実現できるとともに、半導体チップ等に対する糊残りを抑制することが可能となる。 On the other hand, in the entire silicone-based resin contained in the pressure-sensitive adhesive layer 3 of the present embodiment, the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) was set to 40. By setting the range from 0 / 60.0 to 56.0 / 44.0, the following effects can be realized. That is, in the stage before irradiation with light such as ultraviolet rays, the pressure-sensitive adhesive layer 3 is in a state in which a part of the silicone-based resin is crosslinked / cured (first-stage crosslinking reaction) by the thermal polymerization initiator. Therefore, it is possible to impart an appropriate adhesive force and tack force to the pressure-sensitive adhesive layer 3 so that the semiconductor chips and the like, which are cut pieces, do not scatter during dicing. On the other hand, after irradiation with light such as ultraviolet rays, the silicone-based resin of the pressure-sensitive adhesive layer 3 has a silicon atom-bonded alkenyl group content of 7.0 × 10 -7 mol / g or more in the entire silicone-based resin as described above. Since it is configured to have a range of 5.5 × 10 -6 mol / g or less, the silicon atom-bonded alkenyl group of the silicone gum (G) and the silicon atom-bonded hydrogen atom of the cross-linking agent for the silicone-based resin ( The second-stage cross-linking reaction (addition reaction) with the SiH group) proceeds sufficiently. As a result, the curing of the pressure-sensitive adhesive layer 3 further progresses, so that the crosslink density is increased and the cohesive force is further improved, so that a desired decrease in tack force and a fracture mode in the holding force test can be obtained. As a result, after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, good pick-up performance when peeling the obtained semiconductor chip or the like from the adhesive tape 1 can be realized, and adhesive residue on the semiconductor chip or the like is suppressed. It becomes possible to do.
　特に、上記シリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量は、２．９×１０-6ｍｏｌ／ｇ以上４．１×１０-6ｍｏｌ／ｇ以下の範囲とすることが好ましい。この場合、粘着剤層３の凝集力の制御がしやすくなるため、より安定したダイシング特性を有する粘着テープ１を実現することができる。 In particular, the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is preferably in the range of 2.9 × 10 -6 mol / g or more and 4.1 × 10 -6 mol / g or less. In this case, since the cohesive force of the pressure-sensitive adhesive layer 3 can be easily controlled, the pressure-sensitive adhesive tape 1 having more stable dicing characteristics can be realized.
　また、本発明のシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが混合されたシリコーン系樹脂としては、以下に例示する市販の材料を適宜組み合わせて混合調製したものを使用することもできる。ここで、「適宜組み合わせて混合調製したもの」とは、「粘着剤層３のシリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量が７．０×１０-7ｍｏｌ／ｇ以上５．５×１０-6ｍｏｌ／ｇ以下の範囲、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４０．０／６０．０～５６．０／４４．０の範囲となるように、個々の材料を適宜組み合わせ混合調製したもの」を意味する。適宜組み合わせて混合調製するための個々の市販材料としては、例えば、以下の材料（１）～（４）等が挙げられる。 Further, as the silicone-based resin in which the silicone gum (G) and the silicone resin (R) of the present invention are mixed, those prepared by appropriately combining commercially available materials exemplified below can also be used. Here, "a mixture prepared by appropriately combining" means "the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin of the pressure-sensitive adhesive layer 3 is 7.0 × 10 -7 mol / g or more 5.5 ×. In the range of 10 -6 mol / g or less, the mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) is 40.0 / 60.0 to 56.0 / 44.0. It means "a product prepared by appropriately combining and mixing individual materials so as to fall within the range of." Examples of individual commercially available materials for mixing and preparing in appropriate combinations include the following materials (1) to (4).
　ケイ素原子結合アルケニル基を含有するシリコーン系樹脂としては、（１）シリコーンガム（Ｇalk）とシリコーンレジン（Ｒ）が所定の比率で混合された市販の付加反応型シリコーン系粘着剤や、（２）シリコーンガム（Ｇalk）を主成分とする付加反応型シリコーン系離型剤等が挙げられる。また、ケイ素原子結合アルケニル基を含有しないシリコーン系樹脂としては、（３）シリコーンガム（Ｇ0）とシリコーンレジン（Ｒ）とが所定の比率で混合された市販の過酸化物硬化型シリコーン系粘着剤や、（４）市販のシリコーンレジン（Ｒ）の単独物等が挙げられる。本発明において、これら市販の個々の材料を適宜組み合わせて混合調製する場合、少なくとも(２)の付加反応型シリコーン系離型剤を含むことが好ましく、さらにこれに加えて（１）の付加反応型シリコーン系粘着剤を含むことがより好ましい。 Examples of the silicone-based resin containing a silicon atom-bonded alkenyl group include (1) a commercially available addition-reaction silicone-based pressure-sensitive adhesive in which silicone gum (Galk ) and silicone resin (R) are mixed in a predetermined ratio, and (2). ) An addition-reaction type silicone-based mold release agent containing silicone gum (G alk) as a main component can be mentioned. Further, as the silicone-based resin containing no silicon atom-bonded alkenyl group, (3) a commercially available peroxide-curable silicone-based adhesive in which silicone gum (G 0 ) and silicone resin (R) are mixed in a predetermined ratio. Examples thereof include agents and (4) a single product of a commercially available silicone resin (R). In the present invention, when these commercially available individual materials are appropriately combined and prepared, it is preferable to contain at least the addition reaction type silicone release agent of (2), and in addition to this, the addition reaction type of (1). It is more preferable to include a silicone-based pressure-sensitive adhesive.
　上述したように、ケイ素原子結合アルケニル基を含有するシリコーン系樹脂としては、（１）シリコーンガム（Ｇalk）とシリコーンレジン（Ｒ）が所定の比率で混合された市販の付加反応型シリコーン系粘着剤や、（２）シリコーンガム（Ｇalk）を主成分とする市販の付加反応型シリコーン系離型剤等を使用することができる。以下、具体的な市販材料について例示する。 As described above, the silicone-based resin containing the silicon atom-bonded alkenyl group includes (1) a commercially available addition-reaction silicone-based adhesive in which silicone gum (Galk ) and silicone resin (R) are mixed in a predetermined ratio. Agents, (2) commercially available addition-reaction type silicone-based mold release agents containing silicone gum (G alk) as a main component, and the like can be used. Hereinafter, specific commercially available materials will be illustrated.
（１）付加反応型シリコーン系粘着剤
　上記市販の付加反応型シリコーン系粘着剤としては、一般的にシリコーン系粘着テープ用のシリコーン系粘着剤として用いられるものであれば、特に限定されない。具体的には、例えば、信越化学工業株式会社製のＫＲ－３７００、ＫＲ－３７０１、Ｘ－４０－３２３７－１、Ｘ－４０－３２４０、Ｘ－４０－３２９１－１、Ｘ－４０－３２２９、Ｘ－４０－３２７０、Ｘ－４０－３３０６（いずれも商品名）、モメンティブ・パフォーマンス・マテリアルズ社製のＴＳＲ１５１２、ＴＳＲ１５１６、ＸＲ３７－Ｂ９２０４（いずれも商品名）、ダウ・東レ株式会社製のＳＤ４５８０、ＳＤ４５８４、ＳＤ４５８５、ＳＤ４５６０、ＳＤ４５６４、ＳＤ４５６５、ＳＤ４５７０、ＳＤ４５７４、ＳＤ４５７５、ＳＤ４６００ＰＦＣ、ＳＤ４５９３、ＤＣ７６５１ＡＤＨＥＳＩＶＥ（いずれも商品名）等の型番において、白金（Ｐｔ）系触媒および後述する架橋剤が内添されていないタイプを使用することができる。なお、架橋剤が内添されているタイプを使用することもできるが、内添された架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）の含有量が不明の場合は、該含有量は、後述する１Ｈ－ＮＭＲ（核磁気共鳴）スペクトル測定の分析等により求めることができる。 (1) Addition Reaction Silicone Adhesive The commercially available addition reaction silicone adhesive is not particularly limited as long as it is generally used as a silicone adhesive for silicone adhesive tapes. Specifically, for example, KR-3700, KR-3701, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, manufactured by Shin-Etsu Chemical Co., Ltd., X-40-3270, X-40-3306 (all product names), TSR1512, TSR1516, XR37-B9204 (all product names) manufactured by Momentive Performance Materials, SD4580 manufactured by Dow Toray Co., Ltd., SD4584, SD4585, SD4560, SD4564, SD4565, SD4570, SD4574, SD4575, SD4600PFC, SD4593, DC7651ADHESIVE (trade names), etc., in which a platinum (Pt) -based catalyst and a cross-linking agent described later are not added. Can be used. A type in which a cross-linking agent is added can also be used, but if the content of the silicon atom-bonded hydrogen atom (SiH group) contained in the cross-linked agent is unknown, the content is determined by the content. It can be obtained by analysis of 1 H-NMR (nuclear magnetic resonance) spectrum measurement described later.
（２）付加反応型シリコーン系離型剤
　上記市販の付加反応型シリコーン系離型剤としては、一般的に粘着テープ用のシリコーン系離型フィルムの離型処理剤として用いられるものであれば、特に限定されない。具体的には、例えば、ダウ・東レ株式会社製のＬＴＣ７５０Ａ、ＬＴＣ３１０、ＬＴＣ３００Ｂ（いずれも商品名）、信越化学工業株式会社製のＫＳ３６００、ＫＳ７７８（いずれも商品名）、モメンティブ・パフォーマンス・マテリアルズ社製のＴＰＲ６７１０、ＴＰＲ６７００（いずれも商品名）等を使用することができる。この場合も、架橋剤が内添されていないタイプおよび架橋剤が内添されているタイプのいずれを使用してもよく、内添された架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）の含有量は、１Ｈ－ＮＭＲ（核磁気共鳴）スペクトル測定の分析等により求めることができる。 (2) Addition-reaction type silicone-based mold release agent The commercially available addition-reaction type silicone-based mold release agent is as long as it is generally used as a release treatment agent for a silicone-based mold release film for adhesive tapes. There is no particular limitation. Specifically, for example, LTC750A, LTC310, LTC300B (all product names) manufactured by Dow Toray Co., Ltd., KS3600, KS778 (all product names) manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials Co., Ltd. TPR6710, TPR6700 (both are trade names) and the like manufactured by TPR6710 and TPR6700 (both are trade names) can be used. In this case as well, either a type without a cross-linking agent or a type with a cross-linking agent may be used, and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linked agent contained therein may be used. The content can be determined by analysis of 1 H-NMR (nuclear magnetic resonance) spectrum measurement or the like.
　上記市販の付加反応型シリコーン系粘着剤におけるシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率が不明な場合は、該混合比率は、29Ｓｉ－ＮＭＲ（核磁気共鳴）スペクトル測定により、Ｄ単位とＱ単位とのピーク面積比（シリコーンガム：シリコーンレジン＝Ｄ単位：Ｑ単位）から求めることができる。また、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定される、それぞれのピーク面積の比率からも求めることができる。 When the mixing ratio of silicone gum (G) and silicone resin (R) in the above-mentioned commercially available addition reaction type silicone-based pressure-sensitive adhesive is unknown, the mixing ratio is determined by 29 Si-NMR (nuclear magnetic resonance) spectrum measurement. It can be obtained from the peak area ratio of the D unit and the Q unit (silicone gum: silicone resin = D unit: Q unit). It can also be determined from the ratio of each peak area measured by gel permeation chromatography (GPC).
　また、ケイ素原子結合アルケニル基を含有しないシリコーン系樹脂としては、シリコーンガム（Ｇ0）とシリコーンレジン（Ｒ）とが所定の比率で混合された市販の過酸化物硬化型シリコーン系粘着剤や、市販のシリコーンレジン（Ｒ）の単独物等を使用することができる。以下、具体的な市販材料について例示する。 Examples of the silicone-based resin that does not contain a silicon atom-bonded alkenyl group include a commercially available peroxide-curable silicone-based pressure-sensitive adhesive in which silicone gum (G 0) and silicone resin (R) are mixed in a predetermined ratio. A commercially available silicone resin (R) alone can be used. Hereinafter, specific commercially available materials will be illustrated.
（３）過酸化物硬化型シリコーン系粘着剤
　上記市販の過酸化物硬化型シリコーン系粘着剤としては、一般的にシリコーン系粘着テープ用のシリコーン系粘着剤として用いられるものであれば、特に限定されない。具体的には、例えば、信越化学工業株式会社製のＫＲ－１００、ＫＲ－１０１－１０（いずれも商品名）、モメンティブ・パフォーマンス・マテリアルズ社製のＹＲ３３４０、ＹＲ３２８６、ＰＳＡ６１０－ＳＭ、ＸＲ３７－Ｂ６７２２、ＹＦ３８９７（いずれも商品名）、ダウ・東レ株式会社製のＳＨ４２８０、ＳＨ４２８２、ＳＥ４２００、ＢＹ２４－７１７、ＢＹ２４－７１５、Ｑ２－７７３５（いずれも商品名）等が挙げられる。 (3) Peroxide Curable Silicone Adhesive The above-mentioned commercially available peroxide curable silicone adhesive is particularly limited as long as it is generally used as a silicone adhesive for silicone adhesive tapes. Not done. Specifically, for example, KR-100, KR-101-10 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., YR3340, YR3286, PSA610-SM, XR37-B6722 manufactured by Momentive Performance Materials Co., Ltd. , YF3897 (all trade names), SH4280, SH4282, SE4200, BY24-717, BY24-715, Q2-7735 (all trade names) manufactured by Dow Toray Co., Ltd. and the like.
（４）シリコーンレジン
　市販のシリコーンレジン（Ｒ）の単独物としては、具体的には、例えば、モメンティブ・パフォーマンス・マテリアルズ社製のＹＦ３８００、ＸＦ３９０５、ＹＦ３０５７、ＹＦ３８０７、ＹＦ３８０２、ＹＦ３８９７、ＸＣ９６－７２３、２Ｄ ＳＩＬＡＮＯＬ ＦＬＵＩＤ（いずれも商品名）等が挙げられる。 (4) Silicone Resin As a single product of the commercially available silicone resin (R), specifically, for example, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XC96-723, manufactured by Momentive Performance Materials Co., Ltd. 2D SILANOL FLUID (both are trade names) and the like can be mentioned.
　上記市販の過酸化物硬化型シリコーン系粘着剤におけるシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率が不明な場合は、該混合比率は、上記と同様に、29Ｓｉ－ＮＭＲ（核磁気共鳴）スペクトル測定により、Ｄ単位とＱ単位とのピーク面積比（シリコーンガム：シリコーンレジン＝Ｄ単位：Ｑ単位）から求めることができる。また、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定される、それぞれのピーク面積の比率からも求めることができる。 When the mixing ratio of the silicone gum (G) and the silicone resin (R) in the above-mentioned commercially available peroxide-curable silicone-based pressure-sensitive adhesive is unknown, the mixing ratio is 29 Si-NMR (nucleus) in the same manner as described above. It can be obtained from the peak area ratio of D unit and Q unit (silicone gum: silicone resin = D unit: Q unit) by magnetic resonance) spectrum measurement. It can also be determined from the ratio of each peak area measured by gel permeation chromatography (GPC).
　これら市販のシリコーン系樹脂は、上述したように、粘着剤層３のシリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量が７．０×１０-7ｍｏｌ／ｇ以上５．５×１０-6ｍｏｌ／ｇ以下の範囲、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４０．０／６０．０～５６．０／４４．０の範囲となるように適宜組み合わせて混合調製した状態で使用すればよい。これら市販のシリコーン系樹脂を用いる場合の好ましい態様例としては、具体的には、例えば、（ａ）付加反応型シリコーン系粘着剤に付加反応型シリコーン系離型剤を添加したシリコーン系樹脂や、（ｂ）これらにさらに過酸化物硬化型シリコーン系粘着剤および／またはシリコーンレジン（Ｒ）を添加したシリコーン系樹脂を、粘着剤層３を構成する粘着剤組成物の主成分として用いればよい。
　なお、本実施の形態の説明において、「主成分として」とは、粘着剤組成物の固形分を１００質量部とした場合に７５質量部以上を占めることを意味し、好ましくは、９０質量部以上、より好ましくは９５質量部以上である。 As described above, these commercially available silicone-based resins have a silicon atom-bonded alkenyl group content of 7.0 × 10 -7 mol / g or more in the entire silicone-based resin of the pressure-sensitive adhesive layer 3 of 5.5 × 10 -6. In the range of mol / g or less, the mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) is in the range of 40.0 / 60.0 to 56.0 / 44.0. It may be used in a state of being mixed and prepared by appropriately combining them so as to be. Specific examples of preferred embodiments when using these commercially available silicone-based resins include (a) a silicone-based resin obtained by adding an addition-reaction type silicone-based release agent to an addition-reaction type silicone-based pressure-sensitive adhesive. (B) A silicone-based resin to which a peroxide-curable silicone-based pressure-sensitive adhesive and / or a silicone resin (R) is further added may be used as the main component of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3.
In the description of the present embodiment, "as the main component" means that the pressure-sensitive adhesive composition occupies 75 parts by mass or more when the solid content is 100 parts by mass, and preferably 90 parts by mass. The above is more preferably 95 parts by mass or more.
（架橋剤）
　本実施の形態における架橋剤は、紫外線等の光が粘着剤層３に照射されることにより、シリコーン系粘着剤に対する架橋剤としての機能を発現する。すなわち、本実施の形態における架橋剤は、紫外線等の光を粘着剤層３に照射することで、シリコーン系粘着剤中の光感応白金（Ｐｔ）触媒が活性化された際に、シリコーン系樹脂に含まれるシリコーンガム（Ｇalk）が有するケイ素原子結合アルケニル基に対して付加反応させ、粘着剤層３を架橋させるために用いられる。架橋剤によってシリコーン系樹脂が架橋し粘着剤層３が硬化して、架橋密度が高くなるので、粘着剤層３の凝集力が紫外線等の光を照射する前と比較して増大する。
　架橋剤としては、１分子中に少なくとも２個、好ましくは３個以上のケイ素原子結合水素原子（ＳｉＨ基）を有するオルガノポリシロキサン（オルガノハイドロジェンポリシロキサン）が使用される。以下の説明において、ケイ素原子結合水素原子（ＳｉＨ基）を有するオルガノポリシロキサンを、単にオルガノハイドロジェンポリシロキサンと表記する場合がある。 (Crosslinking agent)
The cross-linking agent in the present embodiment exhibits a function as a cross-linking agent for the silicone-based pressure-sensitive adhesive by irradiating the pressure-sensitive adhesive layer 3 with light such as ultraviolet rays. That is, the cross-linking agent in the present embodiment is a silicone-based resin when the light-sensitive platinum (Pt) catalyst in the silicone-based pressure-sensitive adhesive is activated by irradiating the pressure-sensitive adhesive layer 3 with light such as ultraviolet rays. by addition reaction against silicon-bonded alkenyl groups silicone gum (G alk) have contained, used to crosslink the pressure-sensitive adhesive layer 3. Since the silicone-based resin is crosslinked by the cross-linking agent and the pressure-sensitive adhesive layer 3 is cured to increase the cross-linking density, the cohesive force of the pressure-sensitive adhesive layer 3 is increased as compared with that before irradiation with light such as ultraviolet rays.
As the cross-linking agent, an organopolysiloxane (organohydrogenpolysiloxane) having at least two, preferably three or more silicon atom-bonded hydrogen atoms (SiH groups) in one molecule is used. In the following description, an organopolysiloxane having a silicon atom-bonded hydrogen atom (SiH group) may be simply referred to as an organohydrogenpolysiloxane.
　架橋剤として使用されるオルガノハイドロジェンポリシロキサンの分子構造としては、例えば、直鎖状、一部分枝を有する直鎖状、分枝鎖状、網状が例示される。オルガノハイドロジェンポリシロキサンは、２５℃における粘度が１ｍＰａ・ｓ以上５,０００ｍＰａ・ｓ以下の範囲であることが好ましい。なお、上記粘度はＢ型回転粘度計を用いて測定することができる。 Examples of the molecular structure of the organohydrogenpolysiloxane used as a cross-linking agent include linear, linear with partial branches, branched chain, and network. The organohydrogenpolysiloxane preferably has a viscosity at 25 ° C. of 1 mPa · s or more and 5,000 mPa · s or less. The viscosity can be measured using a B-type rotational viscometer.
　架橋剤として使用されるオルガノハイドロジェンポリシロキサンは、従来公知のものをいることができる。例えば、このオルガノハイドロジェンポリシロキサンとしては、下記一般式（５）または一般式（６）で示すものが挙げられるが、これらに限定されるものではない。 As the organohydrogenpolysiloxane used as a cross-linking agent, conventionally known ones can be used. For example, examples of this organohydrogenpolysiloxane include those represented by the following general formula (5) or general formula (6), but are not limited thereto.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　ここで、一般式（５）、一般式（６）において、Ｒ3は、炭素数１～１０の１価炭化水素基であり、ｂは０または１であり、ｐおよびｑは整数であり、オルガノハイドロジェンポリシロキサンの２５℃における粘度が１ｍＰａ・ｓ以上５，０００ｍＰａ・ｓ以下となる値である。ｒは２以上の整数であり、ｓは０以上の整数であり、且つｒ＋ｓ≧３であり、好ましくは８≧ｒ＋ｓ≧３である。オルガノハイドロジェンポリシロキサンは２種以上の混合物であってもよい。 Here, in the general formulas (5) and (6), R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, b is 0 or 1, and p and q are integers. This is a value at which the viscosity of the organohydrogenpolysiloxane at 25 ° C. is 1 mPa · s or more and 5,000 mPa · s or less. r is an integer of 2 or more, s is an integer of 0 or more, and r + s ≧ 3, preferably 8 ≧ r + s ≧ 3. The organohydrogenpolysiloxane may be a mixture of two or more.
　Ｒ3は、炭素数１～１０、好ましくは炭素数１～７の１価炭化水素基である。例えば、メチル基、エチル基、プロピル基、及びブチル基等のアルキル基；シクロヘキシル基等のシクロアルキル基；及びフェニル基、及びトリル基等のアリール基、ビニル基及びアリル基等のアルケニル基が挙げられ、特に、メチル基又はフェニル基が好ましい。 R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. For example, alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl group such as cyclohexyl group; and aryl group such as phenyl group and trill group, and alkenyl group such as vinyl group and allyl group can be mentioned. In particular, a methyl group or a phenyl group is preferable.
　本実施の形態の粘着剤層３における架橋剤として使用されるオルガノハイドロジェンポリシロキサンの含有量は、シリコーンガム（Ｇalk）のケイ素原子結合アルケニル基の含有量およびオルガノハイドロジェンポリシロキサンが有するケイ素原子結合水素原子の含有量との兼ね合いで適切な範囲が変わるので、一概には言えないが、通常は、例えば、粘着剤層３を構成する粘着剤組成物に含まれるシリコーン系樹脂のケイ素原子結合アルケニル基の含有量（総量）に対する、粘着剤組成物に含まれる架橋剤のケイ素原子結合水素原子（ＳｉＨ基）の含有量（総量）のモル比率が２．０以上１０．０以下の範囲となる量が好ましい。 The content of the organohydrogenpolysiloxane used as the cross-linking agent in the pressure-sensitive adhesive layer 3 of the present embodiment is the content of the silicon atom-bonded alkenyl group of the silicone gum (Galk ) and the silicon contained in the organohydrogenpolysiloxane. Since the appropriate range changes depending on the content of the atomic-bonded hydrogen atom, it cannot be said unconditionally, but usually, for example, the silicon atom of the silicone-based resin contained in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 is used. The molar ratio of the content (total amount) of the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent contained in the pressure-sensitive adhesive composition to the content (total amount) of the bonded alkenyl group is in the range of 2.0 or more and 10.0 or less. Is preferable.
　オルガノハイドロジェンポリシロキサンの含有量が上記下限値未満である場合、粘着テープ１に紫外線等の光を照射した際に、シリコーンガムが有するケイ素原子結合アルケニル基と架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間の２段階目の架橋反応（付加反応）による架橋密度の向上が不十分となり、粘着剤が硬化し難く、凝集力が向上しにくくなる。この場合、所望のタック力低下や保持力試験における破壊モードが得られず、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際に、個片化された半導体チップのピックアップ性が悪くなるおそれや、半導体チップ等に糊残りが生じやすくなるおそれがある。 When the content of organohydrogenpolysiloxane is less than the above lower limit, when the adhesive tape 1 is irradiated with light such as ultraviolet rays, the silicon atom-bonded alkenyl group of the silicone gum and the silicon atom-bonded hydrogen atom of the cross-linking agent are present. The improvement of the cross-linking density by the second-stage cross-linking reaction (addition reaction) with the (SiH group) becomes insufficient, the adhesive is hard to cure, and the cohesive force is hard to be improved. In this case, the desired reduction in tack force and the breaking mode in the holding force test cannot be obtained, and after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1. , There is a risk that the pickability of the individualized semiconductor chip will deteriorate, and there is a risk that adhesive residue will easily occur on the semiconductor chip or the like.
　一方、オルガノハイドロジェンポリシロキサンの含有量が上記上限値を超える場合、未反応のオルガノハイドロジェンポリシロキサンが半導体チップを汚染するおそれがある。また、未反応のオルガノハイドロジェンポリシロキサン中のケイ素原子結合水素原子（ＳｉＨ基）が空気中の酸素や水分と反応してＳｉＯＨに変化し、粘着剤層３の被着体に対する粘着力が大きくなって、個片化された半導体チップのピックアップ性が悪くなるおそれがある。 On the other hand, if the content of organohydrogenpolysiloxane exceeds the above upper limit, unreacted organohydrogenpolysiloxane may contaminate the semiconductor chip. Further, the silicon atom-bonded hydrogen atom (SiH group) in the unreacted organohydrogenpolysiloxane reacts with oxygen and water in the air to change to SiOH, and the adhesive force of the pressure-sensitive adhesive layer 3 to the adherend is large. As a result, the pickability of the individualized semiconductor chip may deteriorate.
　本実施の形態の粘着剤層３における架橋剤の含有量は、上述したように、粘着剤層３中のシリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量（総量）に対する架橋剤全体のケイ素原子結合水素原子（ＳｉＨ基）の含有量（総量）のモル比率が上述した範囲内になるように調整すればよい。この範囲を満たす架橋剤の含有量としては、架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）の数によっても異なるが、例えば、粘着剤層３を構成する粘着剤組成物に含まれるシリコーン系樹脂全体の固形分１００質量部に対して、架橋剤を固形分で０．２０質量部以上２０．００質量部以下の範囲となるように添加すればよい。 As described above, the content of the cross-linking agent in the pressure-sensitive adhesive layer 3 of the present embodiment is the silicon of the entire cross-linking agent with respect to the content (total amount) of the silicon atom-bonded alkenyl groups in the entire silicone-based resin in the pressure-sensitive adhesive layer 3. The molar ratio of the content (total amount) of the atomically bonded hydrogen atom (SiH group) may be adjusted to be within the above range. The content of the cross-linking agent satisfying this range varies depending on the number of silicon atom-bonded hydrogen atoms (SiH groups) contained in the cross-linking agent, but for example, the silicone type contained in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3. The cross-linking agent may be added so that the solid content is in the range of 0.20 parts by mass or more and 20.00 parts by mass or less with respect to 100 parts by mass of the solid content of the entire resin.
　粘着剤層３中のシリコーン系樹脂に対する架橋剤の含有量を上述した範囲とすることで、半導体チップをダイシング用粘着テープから剥離する際に、紫外線等の光を粘着剤層３に照射することで、シリコーン系粘着剤中の光感応白金（Ｐｔ）触媒が活性化され、シリコーン系樹脂中のシリコーンガム（Ｇalk）が有するケイ素原子結合アルケニル基と当該シリコーン系樹脂に対する架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間の２段階目の架橋反応（付加反応）が促進されて、架橋密度が高くなり、粘着剤の凝集力が紫外線等の光照射前と比較して大きくなる。この結果、粘着剤層３のタック力が適切に低下し、半導体チップ等を粘着テープ１から剥離する際の良好なピックアップ性を実現できるとともに、半導体チップ等に対する糊残りを抑制することが可能となる。 By setting the content of the cross-linking agent with respect to the silicone-based resin in the pressure-sensitive adhesive layer 3 within the above-mentioned range, the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays when the semiconductor chip is peeled off from the adhesive tape for dying. Then, the photosensitive platinum (Pt) catalyst in the silicone-based pressure-sensitive adhesive is activated, and the silicon atom-bonded alkenyl group contained in the silicone gum (Galk) in the silicone-based resin and the silicon atom contained in the cross-linking agent for the silicone-based resin. The second-stage cross-linking reaction (addition reaction) with the bonded hydrogen atom (SiH group) is promoted, the cross-linking density becomes high, and the cohesive force of the adhesive becomes larger than that before light irradiation such as ultraviolet rays. .. As a result, the tacking force of the pressure-sensitive adhesive layer 3 is appropriately reduced, good pick-up performance when peeling the semiconductor chip or the like from the pressure-sensitive adhesive tape 1 can be realized, and adhesive residue on the semiconductor chip or the like can be suppressed. Become.
　架橋剤としては、一般的に付加反応型シリコーン系粘着剤の架橋剤として使用されるもの、すなわち、１分子中に少なくとも２個のケイ素原子結合水素原子（ＳｉＨ基）を有するオルガノポリシロキサン（オルガノハイドロジェンポリシロキサン）であればよく、特に限定されるものではない。具体的には、例えば、信越化学株式会社製のＸ－９２－１２２（商品名）、ダウ・東レ株式会社製のＢＹ２４－７４１（商品名）等が挙げられる。なお、これら架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）の含有量が不明の場合は、該含有量は、後述する１Ｈ－ＮＭＲ（核磁気共鳴）スペクトル測定の分析等により求めることができる。 The cross-linking agent is generally used as a cross-linking agent for an addition-reaction type silicone-based pressure-sensitive adhesive, that is, an organopolysiloxane (organo) having at least two silicon atom-bonded hydrogen atoms (SiH groups) in one molecule. It may be (hydrogen polysiloxane), and is not particularly limited. Specific examples thereof include X-92-122 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. and BY24-741 (trade name) manufactured by Dow Toray Co., Ltd. If the content of the silicon atom-bonded hydrogen atom (SiH group) contained in these cross-linking agents is unknown, the content can be determined by analysis of 1 H-NMR (nuclear magnetic resonance) spectrum measurement described later. it can.
（光感応白金（Ｐｔ）触媒）
　光感応白金（Ｐｔ）触媒は、紫外線等の光の照射によって、粘着剤層３を構成するシリコーン系樹脂と架橋剤との付加反応（ヒドロシリル化）による硬化を促進させるために用いられる。シリコーン系粘着剤中のシリコーンガム（Ｇalk）が有するケイ素原子結合アルケニル基と架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との付加反応による硬化を促進させるために使用できる光の波長は、２４０ｎｍ以上４００ｎｍ以下の範囲であることが好ましい。
　光感応白金（Ｐｔ）触媒としては、光感応性および反応速度が良好である点から、光活性シクロペンタジエニル白金（ＩＶ）化合物を用いることが好ましい。 (Photosensitive platinum (Pt) catalyst)
The photosensitive platinum (Pt) catalyst is used to accelerate curing by an addition reaction (hydrosilylation) between the silicone resin constituting the pressure-sensitive adhesive layer 3 and a cross-linking agent by irradiation with light such as ultraviolet rays. The wavelength of light that can be used to promote curing by the addition reaction between the silicon atom-bonded alkenyl group of the silicone gum (Galk ) in the silicone-based pressure-sensitive adhesive and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent is , 240 nm or more and preferably 400 nm or less.
As the photosensitive platinum (Pt) catalyst, it is preferable to use a photoactive cyclopentadienyl platinum (IV) compound from the viewpoint of good photosensitivity and reaction rate.
　この光活性シクロペンタジエニル白金（ＩＶ）化合物としては、特に限定されるものではないが、例えば、（シクロペンタジエニル）ジメチルトリメチルシリルメチル白金、（シクロペンタジエニル）ジエチルトリメチルシリルメチル白金、（シクロペンタジエニル）ジプロピルトリメチルシリルメチル白金、（シクロペンタジエニル）ジイソプロピルトリメチルシリルメチル白金、（シクロペンタジエニル）ジアリルトリメチルシリルメチル白金、（シクロペンタジエニル）ジベンジルトリメチルシリルメチル白金、（シクロペンタジエニル）ジメチルトリエチルシリルメチル白金、（シクロペンタジエニル）ジメチルトリプロピルシリルメチル白金、（シクロペンタジエニル）ジメチルトリイソプロピルシリルメチル白金、（シクロペンタジエニル）ジメチルトリフェニルシリルメチル白金、（シクロペンタジエニル）ジメチルジメチルフェニルシリルメチル白金、（シクロペンタジエニル）ジメチルメチルジフェニルシリルメチル白金、（シクロペンタジエニル）ジメチルジメチル（トリメチルシロキシ）シリルメチル白金、（シクロペンタジエニル）ジメチルジメチル（ジメチルビニルシロキシ）シリルメチル白金、［（１’－ナフチル）シクロペンタジエニル］トリメチルシリルメチル白金、［（２’－ナフチル）シクロペンタジエニル］トリメチルシリルメチル白金、［１－メチル－３－（１’－ナフチル）シクロペンタジエニル］トリメチルシリルメチル白金、［１－メチル－３－（２’－ナフチル）シクロペンタジエニル］トリメチルシリルメチル白金、［（４’－ビフェニル）シクロペンタジエニル］トリメチルシリルメチル白金、［１－（４’－ビフェニル）－３－メチルシクロペンタジエニル］トリメチルシリルメチル白金、［（９’－フェナントリル）シクロペンタジエニル］トリメチルシリルメチル白金、［１－メチル－３－（９’－フェナントリル）シクロペンタジエニル］トリメチルシリルメチル白金、［１－（２’－アントラセニル）－３－メチルシクロペンタジエニル］トリメチルシリルメチル白金、［（２’－アントラセニル）シクロペンタジエニル］トリメチルシリルメチル白金、［（１’－ピレニル）シクロペンタジエニル］トリメチルシリルメチル白金、［１－メチル－３－（１’－ピレニル）シクロペンタジエニル］トリメチルシリルメチル白金等が挙げられる。 The photoactive cyclopentadienyl platinum (IV) compound is not particularly limited, but for example, (cyclopentadienyl) dimethyltrimethylsilylmethyl platinum, (cyclopentadienyl) diethyltrimethylsilylmethyl platinum, (cyclo). Pentazienyl) dipropyltrimethylsilylmethyl platinum, (cyclopentadienyl) diisopropyltrimethylsilylmethyl platinum, (cyclopentadienyl) diallyltrimethylsilylmethyl platinum, (cyclopentadienyl) dibenzyltrimethylsilylmethyl platinum, (cyclopentadienyl) Dimethyltriethylsilylmethyl platinum, (cyclopentadienyl) dimethyltripropylsilylmethyl platinum, (cyclopentadienyl) dimethyltriisopropylsilylmethyl platinum, (cyclopentadienyl) dimethyltriphenylsilylmethyl platinum, (cyclopentadienyl) ) Dimethyldimethylphenylsilylmethyl platinum, (cyclopentadienyl) dimethylmethyldiphenylsilylmethyl platinum, (cyclopentadienyl) dimethyldimethyl (trimethylsiloxy) silylmethyl platinum, (cyclopentadienyl) dimethyldimethyl (dimethylvinylsiloxy) silylmethyl Platinum, [(1'-naphthyl) cyclopentadienyl] trimethylsilylmethyl platinum, [(2'-naphthyl) cyclopentadienyl] trimethylsilylmethyl platinum, [1-methyl-3- (1'-naphthyl) cyclopentadi Enyl] trimethylsilylmethyl platinum, [1-methyl-3- (2'-naphthyl) cyclopentadienyl] trimethylsilylmethyl platinum, [(4'-biphenyl) cyclopentadienyl] trimethylsilylmethyl platinum, [1- (4') -Biphenyl) -3-methylcyclopentadienyl] trimethylsilylmethyl platinum, [(9'-phenanthril) cyclopentadienyl] trimethylsilylmethyl platinum, [1-methyl-3- (9'-phenanthril) cyclopentadienyl] Trimethylsilylmethyl platinum, [1- (2'-anthrasenyl) -3-methylcyclopentadienyl] trimethylsilylmethyl platinum, [(2'-anthrasenyl) cyclopentadienyl] trimethylsilylmethyl platinum, [(1'-pyrenyl) cyclo Examples thereof include [pentadienyl] trimethylsilylmethyl platinum and [1-methyl-3- (1'-pyrenyl) cyclopentadienyl] trimethylsilylmethyl platinum.
　上述した化合物中のシクロペンタジエニル環は、メチル、クロロ、フルオロ、トリメチルシリル、トリエチルシリル、ジメチルフェニルシリル、メチルジフェニルシリル、トリフェニルシリル、フェニル、フルオロフェニル、クロロフェニル、メトキシ、ナフチル、ビフェニル、アントラセニル、ピレニル、２－ベンゾイルナフタレン、チオキサントン、２－クロロチオキサントン、２－イソプロピルチオキサントン、アントラキノン、１－クロロアントラキノン、アセトフェノン、ベンゾフェノン、９，１０－ジメチルアントラセン、９，１０－ジクロロアントラセンおよびこれらの中から選択される１以上の基で置換されたシクロペンタジエニル環で置換してもよい。
　また、上述した化合物において、シクロペンタジエニル環がη５－フルオレニル基に置換されていてもよい。 The cyclopentadienyl ring in the above-mentioned compounds includes methyl, chloro, fluoro, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, phenyl, fluorophenyl, chlorophenyl, methoxy, naphthyl, biphenyl, anthracenyl, and the like. Pyrenyl, 2-benzoylnaphthalene, thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, anthracene, 1-chloroanthracene, acetophenone, benzophenone, 9,10-dimethylanthracene, 9,10-dichloroanthracene and selected from these It may be replaced with a cyclopentadienyl ring substituted with one or more groups.
Further, in the above-mentioned compound, the cyclopentadienyl ring may be substituted with a η5-fluorenyl group.
　上述した化合物中のシクロペンタジエニル環としては、置換されていないもの、１以上の芳香族有機基で置換されているもの、１以上の脂肪族有機基で置換されているもの、１以上の芳香族有機基と１以上の脂肪族有機基とで置換されているものが好ましい。また、シクロペンタジエニル環に置換される有機基としては、ナフチル、ビフェニル、アントラセニル、フェナントリルおよびピレニルが好ましい。 The cyclopentadienyl ring in the above-mentioned compound includes one that is not substituted, one that is substituted with one or more aromatic organic groups, one that is substituted with one or more aliphatic organic groups, and one or more. Those substituted with an aromatic organic group and one or more aliphatic organic groups are preferable. Further, as the organic group substituted with the cyclopentadienyl ring, naphthyl, biphenyl, anthracenyl, phenanthryl and pyrenyl are preferable.
　本実施の形態の粘着剤層３における光感応白金（Ｐｔ）触媒の含有量は、紫外線等の光の照射により、シリコーン系粘着剤中のシリコーンガム（Ｇalk）が有するケイ素原子結合アルケニル基と架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との付加反応を促進することができれば、特に限定されるものではない。本実施の形態の粘着剤層３における光感応白金（Ｐｔ）触媒の含有量は、例えば、粘着剤層３を構成する粘着剤組成物中のシリコーン系樹脂全体の固形分１００質量部に対して、固形分で０．１０質量部以上３．００質量部以下の範囲が好ましく、０．２０質量部～１．００質量部の範囲がより好ましい。光感応白金（Ｐｔ）触媒の含有量が０．１０質量部未満である場合、粘着テープ１に紫外線等の光を照射した際に、シリコーンガムが有するケイ素原子結合アルケニル基と架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間の架橋反応（付加反応）が十分に進行せず、架橋密度の向上が不十分となり、粘着剤が硬化し難く、凝集力が向上しにくくなる。この場合、所望のタック力低下や保持力試験における破壊モードが得られず、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際に、個片化された半導体チップのピックアップ性が悪くなるおそれや、半導体チップ等に糊残りが生じやすくなるおそれがある。一方、光感応白金（Ｐｔ）触媒の含有量が３．００質量部を超える場合、上記の架橋反応（付加反応）は十分に進行するため、例えば１０．０質量部の含有量でも粘着テープ１の特性としては特に問題はないが、経済性の観点からは好ましくない。 The content of the photosensitive platinum (Pt) catalyst in the pressure-sensitive adhesive layer 3 of the present embodiment is the same as that of the silicon atom-bonded alkenyl group contained in the silicone gum (Galk) in the silicone-based pressure-sensitive adhesive by irradiation with light such as ultraviolet rays. The cross-linking agent is not particularly limited as long as it can promote the addition reaction with the silicon atom-bonded hydrogen atom (SiH group). The content of the photosensitive platinum (Pt) catalyst in the pressure-sensitive adhesive layer 3 of the present embodiment is, for example, relative to 100 parts by mass of the solid content of the entire silicone-based resin in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3. The solid content is preferably in the range of 0.10 parts by mass or more and 3.00 parts by mass or less, and more preferably in the range of 0.20 parts by mass to 1.00 parts by mass. When the content of the photosensitive platinum (Pt) catalyst is less than 0.10 parts by mass, the silicon atom-bonded alkenyl group contained in the silicone gum and the silicon contained in the cross-linking agent when the adhesive tape 1 is irradiated with light such as ultraviolet rays. The cross-linking reaction (addition reaction) with the atomic-bonded hydrogen atom (SiH group) does not proceed sufficiently, the improvement of the cross-linking density becomes insufficient, the adhesive is hard to cure, and the cohesive force is hard to be improved. In this case, the desired reduction in tack force and the breaking mode in the holding force test cannot be obtained, and after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1. , There is a risk that the pickability of the individualized semiconductor chip will deteriorate, and there is a risk that adhesive residue will easily occur on the semiconductor chip or the like. On the other hand, when the content of the photosensitive platinum (Pt) catalyst exceeds 3.00 parts by mass, the above-mentioned cross-linking reaction (addition reaction) proceeds sufficiently. Therefore, for example, even if the content is 10.0 parts by mass, the adhesive tape 1 There is no particular problem with the characteristics of the above, but it is not preferable from the viewpoint of economic efficiency.
（熱重合開始剤）
　本実施の形態における熱重合開始剤としては、過酸化物、より具体的には有機過酸化物が用いられる。本実施の形態における熱重合開始剤は、紫外線等の光を照射する前の粘着テープ１の粘着剤層３に対して、ダイシングの際に切断片である半導体チップ等の飛散が発生しない適切な粘着力およびタック力を付与させるために用いられる。すなわち、粘着剤層３を形成する際の加熱・乾燥工程で印加される熱により、粘着剤層３中の熱重合開始剤がラジカルを発生する。そして、該ラジカルが、主にシリコーン系樹脂中のシリコーンガム（Ｇ）のメチル基やアルケニル基の一部を攻撃しメチレン鎖を形成して、粘着剤層３を適度に架橋、硬化させる。具体的には、最初にメチル基とアルケニル基とが反応して、これと同時に、またはこれに続いて、メチル基同士や、架橋部分とメチル基との間で架橋反応が進行するものと考えられる。これにより、粘着剤層３に適度な凝集力が付与され、その結果、ダイシングの際に切断片である半導体チップ等の飛散が発生しない適切な粘着力およびタック力を安定して実現することができる。 (Thermal polymerization initiator)
As the thermal polymerization initiator in this embodiment, a peroxide, more specifically, an organic peroxide is used. The thermal polymerization initiator in the present embodiment is suitable so that the semiconductor chip or the like, which is a cut piece, does not scatter with respect to the adhesive layer 3 of the adhesive tape 1 before being irradiated with light such as ultraviolet rays. It is used to impart adhesive strength and tack strength. That is, the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 generates radicals due to the heat applied in the heating / drying step when forming the pressure-sensitive adhesive layer 3. Then, the radical mainly attacks a part of the methyl group and the alkenyl group of the silicone gum (G) in the silicone resin to form a methylene chain, and appropriately crosslinks and cures the pressure-sensitive adhesive layer 3. Specifically, it is considered that the methyl group and the alkenyl group first react with each other, and at the same time or subsequently, the cross-linking reaction proceeds between the methyl groups or between the cross-linked portion and the methyl group. Be done. As a result, an appropriate cohesive force is imparted to the pressure-sensitive adhesive layer 3, and as a result, an appropriate adhesive force and tack force that do not cause scattering of semiconductor chips or the like that are cut pieces during dicing can be stably realized. it can.
　熱重合開始剤として用いられる過酸化物としては、分解して遊離酸素ラジカルを発生するものであれば特に限定されるものではないが、例えば、ジベンゾイルパーオキサイド、４，４’－ジメチルジベンゾイルパーオキサイド、３，３’－ジメチルジベンゾイルパーオキサイド、２，２’－ジメチルジベンゾイルパーオキサイド、２，２’，４，４’－テトラクロロジベンゾイルパーオキサイド、ジイソブチリルパーオキサイド、ジラウロイルパーオキサイド、ジイソナノイルパーオキサイド等の１分間半減期温度が８５℃以上１３５℃以下のジアシルパーオキサイド類；ジクミルパーオキサイド、t－ブチル－クミルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、１，１´－ジ－ｔ－ブチルパーオキシ－３，３，５－トリメチレンシクロヘキサン、１，３－ジ－（ｔ－ブチルパーオキシ）－ジイソプロピルベンゼン等の１分間半減期温度が１７０℃～２００℃のジアルキルパーオキサイド類等が挙げられる。市販品としては、例えば、ジアシルパーオキサイド類として、日油株式会社製のナイパーＢＭＴ－Ｋ４０、ナイパーＢＷ（いずれも商品名）等、ジアルキルパーオキサイド類として、日油株式会社製のパーブチルＣ、パークミルＤ、パーブチルＰ（いずれも商品名）等が挙げられる。 The peroxide used as the thermal polymerization initiator is not particularly limited as long as it decomposes to generate free oxygen radicals, but for example, dibenzoyl peroxide and 4,4'-dimethyldibenzoyl. Peroxide, 3,3'-dimethyldibenzoyl peroxide, 2,2'-dimethyldibenzoyl peroxide, 2,2', 4,4'-tetrachlorodibenzoyl peroxide, diisobutyryl peroxide, dilauroyl peroxide Diacyl peroxides having a 1-minute half-life temperature of 85 ° C or higher and 135 ° C or lower, such as oxides and diisonanoyl peroxides; dicumyl peroxide, t-butyl-cumyl peroxide, 2,5-dimethyl-2,5- Di (t-butylperoxy) hexane, 1,1'-di-t-butylperoxy-3,3,5-trimethylencyclohexane, 1,3-di- (t-butylperoxy) -diisopropylbenzene, etc. Examples thereof include dialkyl peroxides having a 1-minute half-life temperature of 170 ° C. to 200 ° C. Commercially available products include, for example, diacyl peroxides such as NOF BMT-K40 and Nyper BW (both trade names) manufactured by NOF CORPORATION, and dialkyl peroxides such as Perbutyl C manufactured by NOF CORPORATION and Park Mill. Examples thereof include D and perbutyl P (both are trade names).
　上記の過酸化物は、粘着テープ１の基材２の変形温度（耐熱性）、紫外線等の光照射前の状態におけるシリコーンガム（Ｇalk）のアルケニル基の残存量の確保の観点から、１分間半減期温度が８５℃～１３５℃程度であるジアシルパーオキサイド類を用いることが好ましい。すなわち、過酸化物として、ジアシルパーオキサイド類を用いた場合は、ジアルキルパーオキサイド類（１分間半減期温度が１７０℃～２００℃程度）を用いた場合と比較して、粘着剤層３を形成する際の加熱・乾燥工程において、粘着テープ１の基材２が熱変形しにくい低い加熱温度、短い乾燥時間でも分解が可能である。さらにシリコーンガム（Ｇ）のメチル基とアルケニル基との反応よりも、シリコーンガム（Ｇ）のメチル基同士の反応の方が優先的に進行しやすく、紫外線等の光照射時に、架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との付加反応（２段階目の架橋反応）により粘着剤層３の架橋密度をさらに向上させるために必要なシリコーンガム（Ｇalk）のアルケニル基の残存量をより多く確保しておくことができる。 The above peroxide is 1 from the viewpoint of ensuring the deformation temperature (heat resistance) of the base material 2 of the adhesive tape 1 and the residual amount of alkenyl groups of the silicone gum (Galk) in the state before light irradiation such as ultraviolet rays. It is preferable to use diacyl peroxides having a half-life temperature of about 85 ° C. to 135 ° C. per minute. That is, when diacyl peroxides are used as the peroxide, the pressure-sensitive adhesive layer 3 is formed as compared with the case where dialkyl peroxides (with a half-life temperature of about 170 ° C. to 200 ° C. for 1 minute) are used. In the heating / drying step, the base material 2 of the adhesive tape 1 can be decomposed even at a low heating temperature and a short drying time, which are less likely to be thermally deformed. Further, the reaction between the methyl groups of the silicone gum (G) is more likely to proceed preferentially than the reaction between the methyl group and the alkenyl group of the silicone gum (G), and the cross-linking agent has when irradiated with light such as ultraviolet rays. The residual amount of alkenyl group of silicone gum (Galk ) required to further improve the cross-linking density of the pressure-sensitive adhesive layer 3 by the addition reaction (second-stage cross-linking reaction) with the silicon atom-bonded hydrogen atom (SiH group). More can be secured.
　粘着剤層３における上記熱重合開始剤の含有量は、加熱温度・時間、使用する有機過酸化物の分解温度（１分間半減期温度）やシリコーンガム（Ｇ）の混合比率等で異なるため、一概には言えないが、例えば、粘着剤層３中のシリコーン系樹脂全体の固形分１００質量部に対して、固形分で０．１０質量部以上３．００質量部以下の範囲であることが好ましく、０．５０質量部以上２．００質量部以下の範囲であることがより好ましく、０．７０質量部以上１．８０質量部以下の範囲であることが特に好ましい。粘着剤層３における熱重合開始剤の含有量が、粘着剤層３中のシリコーン系樹脂全体の固形分１００質量部に対して固形分で０．１０質量部未満であると、紫外線等の光を照射する前の段階で、粘着剤層３の熱重合開始剤によるシリコーン系樹脂の架橋・硬化（１段階目の架橋反応）が不十分となる。これにより、シリコーン系樹脂全体におけるシリコーンガム（Ｇ）の比率が多い場合に、シリコーンガム（Ｇ）成分に起因して粘着剤層３が柔らかくなるおそれがある。この場合、半導体素子基板等のダイシング時に、ダイシングの振動が粘着剤層３に伝わりやすくなって振動幅が大きくなり、例えば、半導体素子基板が基準位置からずれるおそれがある。そして、これに伴って、個片化された半導体チップに欠け（チッピング）が生じるおそれや、個々の半導体チップごとに大きさのずれが生じるおそれがある。また、粘着剤層３の粘着力やタック力が低下するおそれもある。この場合、該粘着テープ１を半導体素子基板等のダイシングに使用すると、半導体素子基板等を切断する際に、切断片である半導体チップ等が粘着テープ１から剥がれて飛散しやすくなるおそれがある。
　一方、熱重合開始剤の含有量が３．００質量部を超えると、紫外線等の光を照射する前の段階で、熱重合開始剤の種類や加熱温度・時間によっては、シリコーン系樹脂の架橋・硬化（１段階目の架橋反応）が熱重合開始剤により進み過ぎて、粘着剤層３が硬くなり過ぎる場合がある。この場合、粘着テープ１を半導体素子基板等のダイシングに使用すると、半導体素子基板等を切断する際に、切断片である半導体チップ等が粘着テープ１から剥がれて飛散しやすくなるおそれがある。また、熱重合開始剤そのもの、あるいは熱重合開始剤の分解生成物に由来する成分が、被着体に残存して被着体を汚染するおそれがある。 The content of the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 differs depending on the heating temperature / time, the decomposition temperature of the organic peroxide used (1 minute half-life temperature), the mixing ratio of the silicone gum (G), and the like. Although it cannot be said unconditionally, for example, the solid content may be in the range of 0.10 parts by mass or more and 3.00 parts by mass or less with respect to 100 parts by mass of the solid content of the entire silicone-based resin in the pressure-sensitive adhesive layer 3. It is more preferably in the range of 0.50 parts by mass or more and 2.00 parts by mass or less, and particularly preferably in the range of 0.70 parts by mass or more and 1.80 parts by mass or less. When the content of the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 is less than 0.10 parts by mass in terms of solid content with respect to 100 parts by mass in solid content of the entire silicone-based resin in the pressure-sensitive adhesive layer 3, light such as ultraviolet rays is emitted. The cross-linking / curing (first-step cross-linking reaction) of the silicone-based resin by the thermal polymerization initiator of the pressure-sensitive adhesive layer 3 becomes insufficient at the stage before the irradiation. As a result, when the ratio of the silicone gum (G) in the entire silicone resin is large, the pressure-sensitive adhesive layer 3 may be softened due to the silicone gum (G) component. In this case, when dicing the semiconductor element substrate or the like, the vibration of the dicing is easily transmitted to the pressure-sensitive adhesive layer 3, and the vibration width becomes large. For example, the semiconductor element substrate may deviate from the reference position. Along with this, there is a risk that the fragmented semiconductor chips may be chipped (chipping), or that the size of each semiconductor chip may deviate. In addition, the adhesive force and tack force of the pressure-sensitive adhesive layer 3 may decrease. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered.
On the other hand, when the content of the thermal polymerization initiator exceeds 3.00 parts by mass, the silicone-based resin is crosslinked depending on the type of the thermal polymerization initiator and the heating temperature / time before irradiating with light such as ultraviolet rays. -The curing (first-stage cross-linking reaction) may proceed too much due to the thermal polymerization initiator, and the pressure-sensitive adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, the semiconductor chip or the like which is a cut piece may be peeled off from the adhesive tape 1 and easily scattered. In addition, the thermal polymerization initiator itself or a component derived from the decomposition product of the thermal polymerization initiator may remain on the adherend and contaminate the adherend.
　本実施の形態のシリコーン系粘着剤層は、主成分としてシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが混合されたシリコーン系樹脂、シリコーン系樹脂に対する架橋剤として１分子中に少なくとも２個以上のケイ素原子結合水素原子（ＳｉＨ基）を有するオルガノポリシロキサン、熱重合開始剤として過酸化物、および、光感応白金（Ｐｔ）触媒、を含む粘着剤組成物からなるものであるが、本発明の効果を損なわない範囲内で、他の成分を含有してもよい。他の成分としては、凝集力向上剤、補強充填剤、剥離コントロール剤等が挙げられる。 The silicone-based pressure-sensitive adhesive layer of the present embodiment is a silicone-based resin in which silicone gum (G) and silicone resin (R) are mixed as main components, and at least two or more in one molecule as a cross-linking agent for the silicone-based resin. The present invention comprises a pressure-sensitive adhesive composition containing an organopolysiloxane having a silicon atom-bonded hydrogen atom (SiH group), a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst. Other components may be contained as long as the effect of the above is not impaired. Examples of other components include a cohesive force improving agent, a reinforcing filler, a peeling control agent, and the like.
（凝集力向上剤）
　凝集力向上剤は、粘着剤層３の凝集力を向上させるために、必要に応じて用いられる。凝集力向上剤としては、特に限定されるものではないが、例えば、多官能チオールが用いられる。多官能チオールからなる凝集力向上剤としては、例えば、昭和電工株式会社製のカレンズ（登録商標）ＭＴ－ＰＥ１、カレンズＭＴ－ＮＲ１等が挙げられる。 (Cohesive force improver)
The cohesive force improver is used as necessary to improve the cohesive force of the pressure-sensitive adhesive layer 3. The cohesive force improving agent is not particularly limited, but for example, a polyfunctional thiol is used. Examples of the cohesive force improving agent composed of polyfunctional thiol include Karenz (registered trademark) MT-PE1 and Karenz MT-NR1 manufactured by Showa Denko KK.
　ただし、粘着剤層３を構成する粘着剤組成物中のシリコーン系樹脂に多官能チオールは相溶しないため、凝集力向上剤として多官能チオールを使用するためには、シリコーン系樹脂と多官能チオールとの相溶化剤を用いる必要がある。相溶化剤としては、特に限定されるものでないが、例えば、メルカプト基を有するシランカップリング剤である信越化学工業株式会社製のＫＢＭ－８０２、ＫＢＭ－８０３（いずれも商品名）、ダウ・東レ株式会社製のＳＨ６０６２（商品名）等が挙げられる。
　粘着剤層３に凝集力向上剤を用いる場合、凝集力向上剤の添加量は、シリコーン系樹脂全体の固形分１００質量部に対して、固形分で６質量部以下の範囲が好ましい。凝集力向上剤の添加量が、シリコーン系樹脂全体の固形分１００質量部に対して固形分で６質量部を超える場合、相溶化剤を添加してもシリコーン系樹脂と凝集力向上剤である多官能チオールとが相分離するおそれがある。 However, since the polyfunctional thiol is incompatible with the silicone-based resin in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3, in order to use the polyfunctional thiol as a cohesive force improving agent, the silicone-based resin and the polyfunctional thiol are used. It is necessary to use a compatibilizer with. The compatibilizer is not particularly limited, but for example, KBM-802 and KBM-803 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd., which are silane coupling agents having a mercapto group, and Dow Toray. SH6062 (trade name) manufactured by Co., Ltd. and the like can be mentioned.
When a cohesive force improving agent is used for the pressure-sensitive adhesive layer 3, the amount of the cohesive force improving agent added is preferably in the range of 6 parts by mass or less in terms of solid content with respect to 100 parts by mass in solid content of the entire silicone resin. When the amount of the cohesive force improver added exceeds 6 parts by mass in terms of solid content with respect to 100 parts by mass of the solid content of the entire silicone resin, the silicone resin and the cohesive force improver are still present even if the compatibilizer is added. There is a risk of phase separation from the polyfunctional thiol.
（補強充填剤）
　補強充填剤は、粘着剤層３の強度を向上させるために、必要に応じて用いられる。補強充填剤としては、特に限定されるものではないが、例えば、日本アエロジル株式会社製のアエロジル（登録商標）１３０、アエロジル２００、アエロジル３００、株式会社トクヤマ製のレオロシール（登録商標）ＱＳ－１０２、レオロシールＱＳ－３０、ＤＳＬ．ジャパン株式会社製のカープレックス（登録商標）８０、ＰＰＧ製のＨｉ－Ｓｉｌ（登録商標）－２３３－Ｄ等が挙げられる。 (Reinforcing filler)
The reinforcing filler is used, if necessary, in order to improve the strength of the pressure-sensitive adhesive layer 3. The reinforcing filler is not particularly limited, but for example, Aerosil (registered trademark) 130, Aerosil 200, Aerosil 300 manufactured by Nippon Aerosil Co., Ltd., Leoloseal (registered trademark) QS-102 manufactured by Tokuyama Corporation, Leolosil QS-30, DSL. Examples thereof include Carplex (registered trademark) 80 manufactured by Japan Co., Ltd. and Hi-Sil (registered trademark) -233-D manufactured by PPG.
（剥離コントロール剤）
　剥離コントロール剤は、紫外線等の光照射後の粘着剤層３の粘着力をより低減させるために、必要に応じて用いられる。剥離コントロール剤としては、特に限定されるものではないが、例えば、シリコーンオイル等の軽剥離添加剤が挙げられる。但し、剥離コントロール剤の添加量が多い場合、ブリードアウトにより被着体表面が汚染されるおそれがあるので、被着体表面の汚染レベルが許容できる範囲内で添加するのが好ましい。 (Peeling control agent)
The peeling control agent is used as necessary in order to further reduce the adhesive force of the pressure-sensitive adhesive layer 3 after irradiation with light such as ultraviolet rays. The peeling control agent is not particularly limited, and examples thereof include a light peeling additive such as silicone oil. However, if the amount of the peeling control agent added is large, the surface of the adherend may be contaminated by bleeding out, so it is preferable to add the peeling control agent within an acceptable range.
＜粘着剤層の厚さ＞
　粘着剤層３の厚さは、１０μｍ以上１００μｍ以下の範囲が好ましく、２０μｍ以上４０μｍ以下の範囲がより好ましい。粘着剤層３の厚さが１０μｍ未満の場合には、粘着剤層３に含まれるシリコーン系粘着剤の厚さが薄くなるため、粘着テープ１の粘着力が低下しやすい。一方、粘着剤層３の厚さが１００μｍよりも厚い場合には、粘着剤層３の凝集破壊が発生しやすくなるおそれがある。そして、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際に、半導体チップ等に糊残りが生じやすくなるおそれがある。また、半導体素子基板等のダイシング時に、ダイシングの振動が粘着剤層３に伝わりやすくなって振動幅が大きくなり、例えば、半導体素子基板が基準位置からずれるおそれがある。そして、これに伴って、個片化された半導体チップに欠け（チッピング）が生じるおそれや、個々の半導体チップごとに大きさのずれが生じるおそれがある。 <Thickness of adhesive layer>
The thickness of the pressure-sensitive adhesive layer 3 is preferably in the range of 10 μm or more and 100 μm or less, and more preferably in the range of 20 μm or more and 40 μm or less. When the thickness of the pressure-sensitive adhesive layer 3 is less than 10 μm, the thickness of the silicone-based pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 3 becomes thin, so that the adhesive strength of the pressure-sensitive adhesive tape 1 tends to decrease. On the other hand, when the thickness of the pressure-sensitive adhesive layer 3 is thicker than 100 μm, cohesive failure of the pressure-sensitive adhesive layer 3 may easily occur. Then, after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1, there is a possibility that adhesive residue is likely to occur on the semiconductor chip or the like. Further, when dicing a semiconductor element substrate or the like, the vibration of the dicing is easily transmitted to the pressure-sensitive adhesive layer 3, and the vibration width becomes large. For example, the semiconductor element substrate may deviate from the reference position. Along with this, there is a risk that the fragmented semiconductor chips may be chipped (chipping), or that the size of each semiconductor chip may deviate.
＜アンカーコート層＞
　上述したように、本実施の形態の粘着テープ１では、粘着テープ１の製造条件や製造後の粘着テープ１の使用条件等に応じて、基材２と粘着剤層３との間に、基材２の種類に合わせたアンカーコート層を設けたり、コロナ処理等の表面処理を施したりしてもよい。これにより、基材２と粘着剤層３との密着力を改善させることが可能になる。 <Anchor coat layer>
As described above, in the adhesive tape 1 of the present embodiment, a base is formed between the base material 2 and the adhesive layer 3 according to the manufacturing conditions of the adhesive tape 1 and the usage conditions of the adhesive tape 1 after production. An anchor coat layer suitable for the type of the material 2 may be provided, or a surface treatment such as a corona treatment may be applied. This makes it possible to improve the adhesion between the base material 2 and the pressure-sensitive adhesive layer 3.
＜表面処理＞
　基材２の表面（粘着剤層３に対向する面とは反対側の面）には、剥離性改良処理等の表面処理が施されていてもよい。基材２の表面処理に用いられる処理剤としては、特に限定されるものではないが、例えば、長鎖アルキルビニルモノマー重合物、フッ化アルキルビニルモノマー重合物、ポリビニルアルコールカルバメート、アミノアルキド系樹脂等の非シリコーン系の剥離処理剤等を用いることができる。このような非シリコーン系の剥離処理剤としては、例えば、ライオン・スペシャリティ・ケミカルズ株式会社製のピーロイル（登録商標）１０５０、ピーロイル１２００等が挙げられる。 <Surface treatment>
The surface of the base material 2 (the surface opposite to the surface facing the pressure-sensitive adhesive layer 3) may be subjected to a surface treatment such as a peelability improving treatment. The treatment agent used for the surface treatment of the base material 2 is not particularly limited, but for example, a long-chain alkyl vinyl monomer polymer, a fluoroalkyl vinyl monomer polymer, a polyvinyl alcohol carbamate, an aminoalkyd resin and the like. Non-silicone-based release treatment agent and the like can be used. Examples of such a non-silicone-based peeling agent include Peroyl (registered trademark) 1050 and Peroyl 1200 manufactured by Lion Specialty Chemicals Co., Ltd.
＜剥離ライナー＞
　また、粘着剤層３の表面（基材２に対向する面とは反対側の面）には、必要に応じて、剥離ライナーを設けてもよい。剥離ライナーとしては、紙、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等のフィルムに、粘着剤層３に含まれるシリコーン系粘着剤との離型性を高めるための剥離処理を施したものを用いることができる。剥離ライナーの剥離処理に用いる材料としては、特に限定されないが、例えば、フロロアルキル変性シリコーン、長鎖アルキルビニルモノマー重合物、アミノアルキド系樹脂等の材料を用いることができる。 <Peeling liner>
Further, a release liner may be provided on the surface of the pressure-sensitive adhesive layer 3 (the surface opposite to the surface facing the base material 2), if necessary. As the peeling liner, a film such as paper, polyethylene, polypropylene, polyethylene terephthalate, etc., which has been subjected to a peeling treatment for enhancing the releasability from the silicone-based pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 3 can be used. The material used for the peeling treatment of the peeling liner is not particularly limited, and for example, a material such as fluoroalkyl-modified silicone, a long-chain alkylvinyl monomer polymer, or an aminoalkyd-based resin can be used.
＜粘着テープの厚さ＞
　以上説明したような構成を有する粘着テープ１の全体としての厚さは、２０μｍ以上２００μｍ以下の範囲が好ましい。
　粘着テープ１の厚さが２０μｍ未満である場合、粘着テープ１を半導体素子基板等のダイシングに用いた場合に、形成された半導体チップ等を粘着テープ１から剥がし取ることが困難になる場合がある。
　一方、粘着テープ１の厚さが２００μｍを超える場合、粘着テープ１を半導体素子基板に貼り付ける際に、粘着テープ１が半導体素子基板の貼り付け面に形成された凹凸に追従しにくくなる。この場合、粘着テープ１と半導体素子基板等との接着面積が小さくなり、ダイシングの際に半導体チップ等が飛散しやすくなるおそれがある。 <Thickness of adhesive tape>
The overall thickness of the adhesive tape 1 having the structure as described above is preferably in the range of 20 μm or more and 200 μm or less.
When the thickness of the adhesive tape 1 is less than 20 μm, when the adhesive tape 1 is used for dicing a semiconductor element substrate or the like, it may be difficult to peel off the formed semiconductor chip or the like from the adhesive tape 1. ..
On the other hand, when the thickness of the adhesive tape 1 exceeds 200 μm, when the adhesive tape 1 is attached to the semiconductor element substrate, it becomes difficult for the adhesive tape 1 to follow the unevenness formed on the attachment surface of the semiconductor element substrate. In this case, the adhesive area between the adhesive tape 1 and the semiconductor element substrate or the like becomes small, and the semiconductor chip or the like may easily scatter during dicing.
［粘着テープの製造方法］
　続いて、本実施の形態の粘着テープ１の製造方法について説明する。なお、以下で説明する粘着テープ１の製造方法は一例であって、粘着テープ１の製造方法はこれに限定されるものではない。 [Manufacturing method of adhesive tape]
Subsequently, a method for manufacturing the adhesive tape 1 of the present embodiment will be described. The method for producing the adhesive tape 1 described below is an example, and the method for producing the adhesive tape 1 is not limited to this.
　粘着テープ１を製造する際には、まず、トルエンや酢酸エチル等の汎用の有機溶剤に、上述したシリコーン系粘着剤、架橋剤、光感応白金（Ｐｔ）触媒等の成分を溶解させ、粘着剤溶液を得る。続いて、この粘着剤溶液を、必要に応じて表面処理やアンカーコート層の形成を行った基材２の表面に、コンマコータ等を用いて予め定めた厚さになるように塗布する。
　次いで、粘着剤溶液が塗布された基材２を、乾燥炉で加熱することで、粘着剤溶液を乾燥・硬化させ、粘着剤層３を形成する。加熱・乾燥の条件としては、熱重合開始剤の半減期温度等にもよるので一概にはいえないが、例えば、特開２０１２－１０７１２５等に開示されている条件を参照することができる。具体的には、例えば、基材２に粘着剤層３用の粘着剤溶液を塗布し、乾燥炉の前半ゾーン部において、４０～９０℃の温度で段階的に温度を上げて初期乾燥した後、乾燥炉の後半ゾーン部において、１２０～２００℃の温度範囲で、１～５分間の加熱乾燥を行い、ロール状の原反として巻き取ればよいが、この限りではない。
　以上の工程により、図１に示したように、基材２の上に粘着剤層３が積層された粘着テープ１が得られる。本実施の形態では、この段階で、粘着剤層３は、熱重合開始剤によりシリコーン系樹脂の一部が架橋・硬化（１段階目の架橋反応）された状態となっている。 When producing the adhesive tape 1, first, components such as the above-mentioned silicone-based pressure-sensitive adhesive, cross-linking agent, and photosensitive platinum (Pt) catalyst are dissolved in a general-purpose organic solvent such as toluene or ethyl acetate to prepare the pressure-sensitive adhesive. Get the solution. Subsequently, this pressure-sensitive adhesive solution is applied to the surface of the base material 2 which has undergone surface treatment or formation of an anchor coat layer, if necessary, so as to have a predetermined thickness using a comma coater or the like.
Next, the base material 2 coated with the pressure-sensitive adhesive solution is heated in a drying furnace to dry and cure the pressure-sensitive adhesive solution to form the pressure-sensitive adhesive layer 3. The conditions for heating and drying cannot be unconditionally determined because they depend on the half-life temperature of the thermal polymerization initiator, but for example, the conditions disclosed in Japanese Patent Application Laid-Open No. 2012-107125 can be referred to. Specifically, for example, after applying the pressure-sensitive adhesive solution for the pressure-sensitive adhesive layer 3 to the base material 2, the temperature is gradually raised at a temperature of 40 to 90 ° C. in the first half zone portion of the drying furnace to perform initial drying. In the latter half zone of the drying oven, heat drying may be performed for 1 to 5 minutes in a temperature range of 120 to 200 ° C., and the roll-shaped raw material may be wound up, but this is not the case.
By the above steps, as shown in FIG. 1, the adhesive tape 1 in which the adhesive layer 3 is laminated on the base material 2 is obtained. In the present embodiment, at this stage, the pressure-sensitive adhesive layer 3 is in a state in which a part of the silicone-based resin is crosslinked and cured (crosslinking reaction in the first step) by the thermal polymerization initiator.
［粘着テープの使用方法］
　本実施の形態の粘着テープ１は、ＬＥＤ（Light Emitting Diode）やパワー半導体等の半導体素子を有する半導体チップの製造工程において、半導体チップの元となる半導体材料のダイシングに用いられる。 [How to use adhesive tape]
The adhesive tape 1 of the present embodiment is used for dicing a semiconductor material that is a source of a semiconductor chip in a process of manufacturing a semiconductor chip having a semiconductor element such as an LED (Light Emitting Diode) or a power semiconductor.
　具体的には、粘着テープ１は、樹脂やセラミック等からなる基板上にＬＥＤ素子やパワー半導体素子等の半導体素子が複数形成された半導体素子基板をダイシングして、個片化された半導体チップを得るために用いられる。ここで、基板上に複数の半導体素子が形成された半導体素子基板では、通常、半導体素子を温度や湿度等の外部環境から保護するために、半導体素子を覆うように被覆材の一例としての封止樹脂が設けられる場合がある。
　本実施の形態の粘着テープ１は、特に封止樹脂が設けられた半導体素子基板のダイシングにより好ましく用いることができる。 Specifically, the adhesive tape 1 is a semiconductor chip formed by dicing a semiconductor element substrate in which a plurality of semiconductor elements such as LED elements and power semiconductor elements are formed on a substrate made of resin, ceramic, or the like. Used to obtain. Here, in a semiconductor element substrate in which a plurality of semiconductor elements are formed on the substrate, usually, in order to protect the semiconductor element from an external environment such as temperature and humidity, a seal is used as an example of a coating material so as to cover the semiconductor element. A stop resin may be provided.
The adhesive tape 1 of the present embodiment can be preferably used by dicing a semiconductor device substrate provided with a sealing resin.
　封止樹脂が設けられた半導体素子基板を切断して複数の半導体チップを得るための方法としては、例えば以下のような方法が従来、知られている。
　まず、半導体素子基板の基板側からダイシング用の粘着テープを貼り付けるとともに、ダイサー等により半導体素子基板を半導体素子が形成される側から切断する。そして、切断により形成されたそれぞれの半導体チップを粘着テープから剥がし取ることで、複数の半導体チップを得る。 As a method for cutting a semiconductor element substrate provided with a sealing resin to obtain a plurality of semiconductor chips, for example, the following method is conventionally known.
First, an adhesive tape for dicing is attached from the substrate side of the semiconductor element substrate, and the semiconductor element substrate is cut from the side where the semiconductor element is formed by a dicer or the like. Then, each semiconductor chip formed by cutting is peeled off from the adhesive tape to obtain a plurality of semiconductor chips.
　しかし、このように半導体素子基板の基板側からダイシング用の粘着テープを貼り付け半導体素子基板の切断を行った場合、切断面（半導体チップの基板側面）に欠落が生じる所謂ダレが発生したり、切断面が粗くなったりする等の課題がある。
　そこで、近年では、このような課題を解決するために、半導体素子基板に対して、基板側だけでなく、半導体素子が形成される側、すなわち半導体素子を封止する封止樹脂側からダイシング用の粘着テープを貼り付けて、半導体素子基板を切断する方法が提案されている。 However, when the adhesive tape for dicing is attached from the substrate side of the semiconductor element substrate in this way to cut the semiconductor element substrate, so-called sagging may occur in which the cut surface (side surface of the semiconductor chip substrate) is chipped. There is a problem that the cut surface becomes rough.
Therefore, in recent years, in order to solve such a problem, not only the substrate side but also the side where the semiconductor element is formed, that is, the sealing resin side for sealing the semiconductor element, is used for dicing with respect to the semiconductor element substrate. A method of cutting a semiconductor device substrate by attaching the adhesive tape of the above has been proposed.
　ここで、ＬＥＤやパワー半導体等の半導体素子用の封止樹脂としては、従来、電気特性や耐熱性に優れるエポキシ樹脂が利用されているが、エポキシ樹脂は、高出力のＬＥＤやパワー半導体に使用した場合、短波長のＬＥＤに使用した場合、または半導体チップの使用環境等によって、変色しやすいという問題がある。 Here, as a sealing resin for semiconductor elements such as LEDs and power semiconductors, epoxy resins having excellent electrical characteristics and heat resistance have been conventionally used, but epoxy resins are used for high-power LEDs and power semiconductors. If this is the case, there is a problem that the color is easily discolored when used for a short-wavelength LED, or depending on the usage environment of the semiconductor chip.
　これに対し、エポキシ樹脂と比較して熱や光による変色が起こりにくいという理由で、近年では、ＬＥＤやパワー半導体等の半導体素子用の封止樹脂としてシリコーン樹脂が用いられる場合が多い。より具体的には、官能基としてメチル基およびフェニル基の双方または一方を含有するシリコーン樹脂、すなわちメチル基を含有するシリコーン樹脂、フェニル基を含有するシリコーン樹脂、メチル基とフェニル基との双方を含有するシリコーン樹脂が用いられる場合が多い。 On the other hand, in recent years, silicone resins are often used as sealing resins for semiconductor elements such as LEDs and power semiconductors because discoloration due to heat or light is less likely to occur compared to epoxy resins. More specifically, a silicone resin containing both or one of a methyl group and a phenyl group as a functional group, that is, a silicone resin containing a methyl group, a silicone resin containing a phenyl group, and both a methyl group and a phenyl group. In many cases, the contained silicone resin is used.
　半導体素子の封止樹脂としてシリコーン樹脂を用いることで、熱や光による封止樹脂の変色を抑制することができる。また、シリコーン樹脂は、光透過率が８８％以上（波長４００～８００ｎｍ）と高く、屈折率を１．４１以上１．５７以下の範囲で調整できる。このため、半導体素子がＬＥＤである場合、封止樹脂として、より屈折率の高いシリコーン樹脂を用いることで、ＬＥＤからの放射光を効率的にパッケージの外部に取り出すことができる。上述したシリコーン樹脂の中でも、フェニル基を含有するシリコーン樹脂を用いることで、メチル基を含有するシリコーン樹脂を用いる場合と比べて、封止材の屈折率をより高くすることができるので、更なる放射光の効率化を図ることができる。 By using a silicone resin as the sealing resin for the semiconductor element, discoloration of the sealing resin due to heat or light can be suppressed. Further, the silicone resin has a high light transmittance of 88% or more (wavelength 400 to 800 nm), and the refractive index can be adjusted in the range of 1.41 or more and 1.57 or less. Therefore, when the semiconductor element is an LED, the synchrotron radiation from the LED can be efficiently taken out of the package by using a silicone resin having a higher refractive index as the sealing resin. Among the above-mentioned silicone resins, by using a silicone resin containing a phenyl group, the refractive index of the encapsulant can be made higher than that in the case of using a silicone resin containing a methyl group. The efficiency of emitted light can be improved.
　メチル基を含有するシリコーン樹脂としては、特に限定されるものではないが、例えば、信越化学工業株式会社製のＫＥＲ－２３００、ＫＥＲ－２４６０、ＫＥＲ－２５００Ｎ、ＫＥＲ－２６００、ＫＥＲ－２７００、ＫＥＲ－２９００、Ｘ－３２－２５２８（いずれも商品名）、モメンティブ・パフォーマンス・マテリアルズ社製のＩＶＳ４３１２、ＩＶＳ４３１２、ＸＥ１４－Ｃ２０４２、ＩＶＳ４５４２、ＩＶＳ４５４６、ＩＶＳ４６２２、ＩＶＳ４６３２、ＩＶＳ４７４２、ＩＶＳ４７５２、ＩＶＳＧ３４４５、ＩＶＳＧ０８１０、ＩＶＳＧ５７７８、ＸＥ１３－Ｃ２４７９、ＩＶＳＭ４５００（いずれも商品名）、ダウ・東レ株式会社製のＯＥ－６３５１、ＯＥ－６３３６、ＯＥ－６３０１（いずれも商品名）等が挙げられる。
　メチル基とフェニル基とを含有するシリコーン樹脂としては、特に限定されるものではないが、例えば、信越化学工業株式会社製ＫＥＲ－６０７５、ＫＥＲ－６１５０、ＫＥＲ－６０２０（いずれも商品名）等が挙げられる。
　フェニル基を含有するシリコーン樹脂としては、特に限定されるものではないが、例えば、信越化学工業株式会社製ＫＥＲ－６１１０、ＫＥＲ－６０００、ＫＥＲ－６２００、ＡＳＰ－１１１１、ＡＳＰ－１０６０、ＡＳＰ－１１２０、ＡＳＰ－１０５０Ｐ（いずれも商品名）、モメンティブ・パフォーマンス・マテリアルズ社製のＸＥ１４－Ｃ２５０８（商品名）、ダウ・東レ株式会社製のＯＥ－６５２０、ＯＥ－６５５０、ＯＥ－６６３１、ＯＥ－６６３６、ＯＥ－６６３５、ＯＥ－６６３０（いずれも商品名）等が挙げられる。 The silicone resin containing a methyl group is not particularly limited, but for example, KER-2300, KER-2460, KER-2500N, KER-2600, KER-2700, KER- of Shin-Etsu Chemical Co., Ltd. 2900, X-32-2528 (all trade names), IVS4312, IVS4312, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, IVSG3445, IVSG0810, IVSG5778, XE13 manufactured by Momentive Performance Materials. -C2479, IVSM4500 (all trade names), OE-6351, OE-6336, OE-6301 (all trade names) manufactured by Dow Toray Co., Ltd. and the like can be mentioned.
The silicone resin containing a methyl group and a phenyl group is not particularly limited, and examples thereof include KER-6075, KER-6150, and KER-6020 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Can be mentioned.
The silicone resin containing a phenyl group is not particularly limited, but for example, KER-6110, KER-6000, KER-6200, ASP-1111, ASP-1060, ASP-1120 manufactured by Shin-Etsu Chemical Co., Ltd. , ASP-1050P (trade name), XE14-C2508 (trade name) manufactured by Momentive Performance Materials, OE-6520, OE-6550, OE-6331, OE-6636 manufactured by Dow Toray Co., Ltd. , OE-6635, OE-6630 (all are trade names) and the like.
　ところで、従来、半導体素子を切断するために使用されるダイシング用の粘着テープとしては、例えば粘着剤層がアクリル樹脂系の粘着剤からなる粘着テープが使用されている。
　しかし、このような従来の粘着テープを、半導体素子基板の半導体素子が形成される側（封止樹脂側）から貼り付けて半導体素子基板のダイシングを行うと、例えば、封止樹脂と粘着テープとの粘着力が不十分な場合には、ダイシング時に半導体チップが飛散する等の問題が生じるおそれがある。 By the way, conventionally, as an adhesive tape for dicing used for cutting a semiconductor element, for example, an adhesive tape in which the adhesive layer is made of an acrylic resin-based adhesive is used.
However, when such a conventional adhesive tape is attached from the side where the semiconductor element of the semiconductor element substrate is formed (sealing resin side) and the semiconductor element substrate is diced, for example, the sealing resin and the adhesive tape are obtained. If the adhesive strength of the semiconductor chip is insufficient, problems such as scattering of semiconductor chips during dicing may occur.
　特に、上述したシリコーン樹脂は、例えば封止樹脂として従来用いられるエポキシ樹脂等と比較して離型性が高い性質を有している。したがって、封止樹脂としてシリコーン樹脂を使用した半導体素子基板に対して、例えば粘着剤層がアクリル樹脂系の粘着剤からなる粘着テープを貼り付けた場合には、封止樹脂であるシリコーン樹脂と粘着テープとの接着力が小さくなりやすい。この結果、半導体素子基板のダイシングの際に半導体チップの飛散等の問題がより生じやすくなる。 In particular, the above-mentioned silicone resin has a property of higher releasability as compared with, for example, an epoxy resin conventionally used as a sealing resin. Therefore, for example, when an adhesive tape whose adhesive layer is an acrylic resin-based adhesive is attached to a semiconductor element substrate using a silicone resin as a sealing resin, it adheres to the silicone resin which is the sealing resin. Adhesive strength with the tape tends to be small. As a result, problems such as scattering of semiconductor chips are more likely to occur during dicing of the semiconductor element substrate.
　これに対し、本実施の形態の粘着テープ１は、上述したように、粘着剤層３がシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが適切な比率で混合され、且つ所定量のケイ素原子結合アルケニル基を有するシリコーン系樹脂と熱重合開始剤とを含む粘着剤組成物により構成されることで、粘着剤層３は、熱重合開始剤によりシリコーン系樹脂の一部が架橋・硬化（１段階目の架橋反応）された状態となっているため、半導体素子基板のダイシングを行う場合に、シリコーン樹脂からなる封止樹脂側から貼り付けて使用した場合であっても、半導体素子基板の封止樹脂に対する粘着力およびタック力を安定且つ良好に保つことができる。そして、従来の粘着テープと比較して、半導体素子基板のダイシングを行う場合に、半導体チップの飛散等の発生を抑制することができる。
　一方で、粘着剤層３を構成する粘着剤組成物が上述したシリコーン系樹脂とともに光感応白金（Ｐｔ）触媒および架橋剤を含有することで、紫外線等の光を照射することによってシリコーン系樹脂中の光感応白金（Ｐｔ）触媒が活性化され、シリコーン系樹脂中のシリコーンガム（Ｇalk）が有するケイ素原子結合アルケニル基と当該シリコーン系樹脂に対する架橋剤が有するケイ素原子結合水素原子（ＳｉＨ基）との間の２段階目の架橋反応（付加反応）が促進され架橋密度が高くなるので、粘着剤の凝集力が紫外線等の光照射前と比較してさらに大きくなる。この結果、粘着剤層３のタック力が適切に低下し、さらに保持力試験における破壊モードが「界面剥離」あるいは保持力試験において「落下しない」ものとなる。これにより、半導体チップ等を粘着テープ１から剥離する際の良好なピックアップ性を実現できるとともに、半導体チップ等に対する糊残りを抑制することが可能となる。 On the other hand, in the adhesive tape 1 of the present embodiment, as described above, the adhesive layer 3 is a mixture of silicone gum (G) and silicone resin (R) in an appropriate ratio, and a predetermined amount of silicon atoms. By being composed of a pressure-sensitive adhesive composition containing a silicone-based resin having a bonded alkenyl group and a thermal polymerization initiator, a part of the silicone-based resin is crosslinked and cured by the thermal polymerization initiator in the pressure-sensitive adhesive layer 3 (1). Since it is in the state of being crosslinked at the stage), the semiconductor element substrate is sealed even when it is used by pasting it from the sealing resin side made of silicone resin when dying the semiconductor element substrate. It is possible to maintain stable and good adhesive force and tack force with respect to the stop resin. Then, as compared with the conventional adhesive tape, it is possible to suppress the occurrence of scattering of the semiconductor chip when dicing the semiconductor element substrate.
On the other hand, the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 3 contains a photosensitive platinum (Pt) catalyst and a cross-linking agent together with the above-mentioned silicone-based resin, so that the silicone-based resin is irradiated with light such as ultraviolet rays. The photosensitive platinum (Pt) catalyst is activated, and the silicon atom-bonded alkenyl group of the silicone gum (Galk ) in the silicone-based resin and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent for the silicone-based resin. Since the second-stage cross-linking reaction (addition reaction) between the two is promoted and the cross-linking density is increased, the cohesive force of the adhesive is further increased as compared with that before light irradiation such as ultraviolet rays. As a result, the tack force of the pressure-sensitive adhesive layer 3 is appropriately reduced, and the fracture mode in the holding force test is "interfacial peeling" or "does not fall" in the holding force test. As a result, it is possible to realize good pick-up performance when peeling the semiconductor chip or the like from the adhesive tape 1, and it is possible to suppress adhesive residue on the semiconductor chip or the like.
　以下、本実施の形態の粘着テープ１の使用方法、および本実施の形態の粘着テープ１を使用した半導体チップの製造方法について、詳細に説明する。図２（ａ）～（ｅ）は、本実施の形態の粘着テープ１を使用した半導体チップの製造方法を示した図である。
　なお、ここでは、粘着テープ１を用いて、半導体素子としてＬＥＤ素子を有する半導体チップを製造する場合を例に挙げて説明する。また、以下で説明する方法は、粘着テープ１の使用方法、および粘着テープ１を使用した半導体チップの製造方法の一例であって、以下の方法に限定されるものではない。 Hereinafter, a method of using the adhesive tape 1 of the present embodiment and a method of manufacturing a semiconductor chip using the adhesive tape 1 of the present embodiment will be described in detail. 2 (a) to 2 (e) are views showing a method of manufacturing a semiconductor chip using the adhesive tape 1 of the present embodiment.
Here, a case where a semiconductor chip having an LED element as a semiconductor element is manufactured by using the adhesive tape 1 will be described as an example. Further, the method described below is an example of a method of using the adhesive tape 1 and a method of manufacturing a semiconductor chip using the adhesive tape 1, and is not limited to the following methods.
　本実施の形態では、まず、例えば樹脂材料やセラミック等からなる基板１０１上に、複数の半導体素子１０２を積載し、半導体素子基板１００を作製する。なお、半導体素子１０２は、例えばＬＥＤ素子であって、図示は省略するが、例えば通電により発光する発光層等を含む複数の半導体層が積層されて構成され、上部には電極が形成されている。
　次に、半導体素子基板１００の基板１０１上に形成された複数の半導体素子を、シリコーン系樹脂からなる封止樹脂１０３で封止する（封止工程）。なお、この例では、複数の半導体素子１０２を封止樹脂１０３によりまとめて封止しているが、個々の半導体素子１０２を封止樹脂１０３により個別に封止してもよい。 In the present embodiment, first, a plurality of semiconductor elements 102 are mounted on a substrate 101 made of, for example, a resin material or ceramic, to manufacture a semiconductor element substrate 100. The semiconductor element 102 is, for example, an LED element, and although not shown, the semiconductor element 102 is configured by stacking a plurality of semiconductor layers including, for example, a light emitting layer that emits light when energized, and an electrode is formed on the upper portion. ..
Next, a plurality of semiconductor elements formed on the substrate 101 of the semiconductor element substrate 100 are sealed with a sealing resin 103 made of a silicone-based resin (sealing step). In this example, the plurality of semiconductor elements 102 are collectively sealed with the sealing resin 103, but the individual semiconductor elements 102 may be individually sealed with the sealing resin 103.
　続いて、図２（ａ）に示すように、粘着テープ１の粘着剤層３が半導体素子基板１００の封止樹脂１０３と対向するように、粘着テープ１と半導体素子基板１００とを貼り合わせる（貼付工程）。
　次いで、図２（ｂ）、（ｃ）に示すように、粘着テープ１と半導体素子基板１００とを貼り合わせた状態で、切断予定ラインＸに沿って、半導体素子基板１００をダイサーなどによって切断する（切断工程）。この例では、粘着テープ１が貼り付けられた半導体素子基板１００を、基板１０１側から切断している。また、図２（ｃ）に示すように、この例では、半導体素子基板１００を厚さ方向に全て切り込む所謂フルカットを行っている。 Subsequently, as shown in FIG. 2A, the adhesive tape 1 and the semiconductor element substrate 100 are bonded together so that the adhesive layer 3 of the adhesive tape 1 faces the sealing resin 103 of the semiconductor element substrate 100 ( Pasting process).
Next, as shown in FIGS. 2 (b) and 2 (c), the semiconductor element substrate 100 is cut by a dicer or the like along the planned cutting line X in a state where the adhesive tape 1 and the semiconductor element substrate 100 are bonded together. (Cutting process). In this example, the semiconductor element substrate 100 to which the adhesive tape 1 is attached is cut from the substrate 101 side. Further, as shown in FIG. 2C, in this example, a so-called full cut is performed in which the semiconductor element substrate 100 is completely cut in the thickness direction.
　続いて、図２（ｄ）に示すように、半導体素子基板１００に貼り付けられた粘着テープ１に対して、基材２側から紫外線等の光を照射する（照射工程）。上述したように、基材２は、紫外線等の光を透過する材質により構成されている。したがって、粘着テープ１に対して基材２側から紫外線等の光を照射することで、基材２を透過して粘着剤層３に紫外線等の光が照射されることになる。
　本実施の形態の粘着テープ１では、粘着剤層３が光感応白金（Ｐｔ）触媒を有することから、粘着剤層３に紫外線等の光が照射されることで、光感応白金（Ｐｔ）触媒が活性化し、粘着剤層３におけるケイ素原子結合アルケニル基を含有するシリコーン系樹脂と架橋剤との２段階目の架橋反応（付加反応）が促進される。これにより、紫外線等の光を照射する前と比べて粘着剤層３における架橋密度、すなわち凝集力がさらに増大し、粘着剤層３のタック力が低下する。 Subsequently, as shown in FIG. 2D, the adhesive tape 1 attached to the semiconductor element substrate 100 is irradiated with light such as ultraviolet rays from the base material 2 side (irradiation step). As described above, the base material 2 is made of a material that transmits light such as ultraviolet rays. Therefore, by irradiating the adhesive tape 1 with light such as ultraviolet rays from the base material 2 side, the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays through the base material 2.
In the pressure-sensitive adhesive tape 1 of the present embodiment, since the pressure-sensitive adhesive layer 3 has a light-sensitive platinum (Pt) catalyst, the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays to obtain a light-sensitive platinum (Pt) catalyst. Is activated, and the second-stage cross-linking reaction (addition reaction) between the silicone-based resin containing the silicon atom-bonded alkenyl group in the pressure-sensitive adhesive layer 3 and the cross-linking agent is promoted. As a result, the crosslink density in the pressure-sensitive adhesive layer 3, that is, the cohesive force is further increased as compared with before irradiation with light such as ultraviolet rays, and the tack force of the pressure-sensitive adhesive layer 3 is reduced.
　続いて、半導体素子基板１００を切断することにより形成された半導体チップ２００を、粘着テープ１から剥がし取る（ピックアップする）ことで、図２（ｅ）に示すように、個片化された半導体チップ２００を得ることができる（剥離工程）。 Subsequently, the semiconductor chip 200 formed by cutting the semiconductor element substrate 100 is peeled off (picked up) from the adhesive tape 1, and as shown in FIG. 2E, the semiconductor chip is separated into individual pieces. 200 can be obtained (peeling step).
　上述したように、本実施の形態の粘着テープ１は、粘着剤層３がシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが適切な比率で混合され、且つ所定量のケイ素原子結合アルケニル基を有するシリコーン系樹脂と熱重合開始剤とを含む粘着剤組成物により構成される。これにより、粘着テープ１をダイシングに使用する場合に、半導体素子基板１００に対する粘着テープ１の粘着力およびタック力を安定且つ良好に保つことができる。
　特に、近年では、半導体素子１０２を封止する封止樹脂１０３として、離型性の高いシリコーン樹脂を使用することが多い。これに対し、本実施の形態の粘着テープ１は、上述した構成を有することで、シリコーン樹脂からなる封止樹脂１０３に対しても良好な粘着力およびタック力を有する。
　この結果、本実施の形態の粘着テープ１は、半導体素子基板１００のダイシングに使用した場合に、半導体チップ２００の飛散を抑制することができる。 As described above, in the pressure-sensitive adhesive tape 1 of the present embodiment, the pressure-sensitive adhesive layer 3 is a mixture of silicone gum (G) and silicone resin (R) in an appropriate ratio, and has a predetermined amount of silicon atom-bonded alkenyl groups. It is composed of a pressure-sensitive adhesive composition containing a silicone-based resin and a thermal polymerization initiator. Thereby, when the adhesive tape 1 is used for dicing, the adhesive force and the tack force of the adhesive tape 1 with respect to the semiconductor element substrate 100 can be kept stable and good.
In particular, in recent years, a silicone resin having high releasability is often used as the sealing resin 103 for sealing the semiconductor element 102. On the other hand, the adhesive tape 1 of the present embodiment has a good adhesive force and a tack force with respect to the sealing resin 103 made of a silicone resin by having the above-mentioned structure.
As a result, the adhesive tape 1 of the present embodiment can suppress the scattering of the semiconductor chip 200 when used for dicing the semiconductor element substrate 100.
　さらに、本実施の形態の粘着テープ１の粘着剤層３を構成するシリコーン系樹脂を含んでなる粘着剤組成物は、上述したように封止樹脂１０３と良好な粘着力を有する一方で、離型性が高い性質を有している。
　すなわち、本実施の形態の粘着テープ１は、例えば紫外線等の光の照射により粘着剤層３中のケイ素原子結合アルケニル基を含有するシリコーン系樹脂と架橋剤との付加反応を促進する光感応白金（Ｐｔ）触媒を含んでいる。そして、切断工程の後、剥離工程の前に基材２を介して粘着剤層３に紫外線等の光を照射することで、光感応白金（Ｐｔ）触媒が活性化され、粘着剤層３においてケイ素原子結合アルケニル基を含有するシリコーン系樹脂と架橋剤との付加反応を促進させて、紫外線等の光を照射する前と比べて粘着剤層３における架橋密度をさらに高め、すなわち凝集力をさらに増大させ、粘着剤層３のタック力を低下させることができる。これにより、剥離工程において、半導体素子基板１００のダイシングにより得られた半導体チップ２００を粘着テープ１から剥がし取る（ピックアップする）際に、半導体チップ２００に粘着剤が付着する所謂糊残りの発生を抑制することができる。また、半導体チップ２００を粘着テープ１から剥離する際の良好なピックアップ性を実現できる。 Further, the pressure-sensitive adhesive composition containing the silicone-based resin constituting the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive tape 1 of the present embodiment has good adhesive strength with the sealing resin 103 as described above, while being separated. It has a high type property.
That is, the adhesive tape 1 of the present embodiment is a photosensitive platinum that promotes an addition reaction between a silicone-based resin containing a silicon atom-bonded alkenyl group in the adhesive layer 3 and a cross-linking agent by irradiation with light such as ultraviolet rays. Contains (Pt) catalyst. Then, after the cutting step and before the peeling step, the pressure-sensitive adhesive layer 3 is irradiated with light such as ultraviolet rays via the base material 2, so that the light-sensitive platinum (Pt) catalyst is activated and the pressure-sensitive adhesive layer 3 is formed. By promoting the addition reaction between the silicone resin containing a silicon atom-bonded alkenyl group and the cross-linking agent, the cross-linking density in the pressure-sensitive adhesive layer 3 is further increased, that is, the cohesive force is further increased as compared with before irradiation with light such as ultraviolet rays. It can be increased and the tack force of the pressure-sensitive adhesive layer 3 can be reduced. As a result, in the peeling step, when the semiconductor chip 200 obtained by dicing the semiconductor element substrate 100 is peeled (picked up) from the adhesive tape 1, the generation of so-called adhesive residue on the semiconductor chip 200 is suppressed. can do. In addition, good pick-up performance when peeling the semiconductor chip 200 from the adhesive tape 1 can be realized.
　なお、上記では、基板上に複数の半導体素子が形成された半導体素子基板に対して、粘着テープ１を封止樹脂側から貼り付けてダイシングを行い、個片化された半導体チップを得る方法について説明した。しかしながら、本実施の形態の粘着テープ１の用途は、これに限定されるものではない。
　本実施の形態の粘着テープ１は、例えばチップスケールパッケージＬＥＤの製造において、複数のＬＥＤ素子が被覆材の一例としての蛍光体に被覆された半導体材料をダイシングして、個片化されたチップスケールパッケージＬＥＤを得るために用いてもよい。なお、蛍光体とは、樹脂材料やセラミック等に蛍光材料が分散された部材である。 In the above description, the method for obtaining an individualized semiconductor chip by attaching an adhesive tape 1 to a semiconductor element substrate on which a plurality of semiconductor elements are formed from the sealing resin side and performing dicing. explained. However, the use of the adhesive tape 1 of the present embodiment is not limited to this.
The adhesive tape 1 of the present embodiment is, for example, in the manufacture of a chip scale package LED, in which a plurality of LED elements are diced from a semiconductor material coated with a phosphor as an example of a coating material, and the chip scale is individualized. It may be used to obtain a package LED. The phosphor is a member in which the fluorescent material is dispersed in a resin material, ceramic, or the like.
　近年、チップスケールパッケージＬＥＤの小型化に伴い、ダイシング時に個片化されたチップスケールパッケージＬＥＤが飛散しやすい傾向がある。これに対し、上述した構成を有する本実施の形態の粘着テープ１を用いることで、蛍光体と粘着剤層３との接着力を良好に保つことが可能となり、個片化されたチップスケールパッケージＬＥＤの飛散を抑制することができる。
　また、ダイシング後、粘着剤層３に紫外線等の光を照射してタック力を低下させることで、粘着テープ１から個片化されたチップスケールパッケージＬＥＤを剥離しやすくなるとともに、剥離したチップスケールパッケージＬＥＤに対する糊残りの発生を抑制することができる。 In recent years, with the miniaturization of chip scale package LEDs, the chip scale package LEDs that have been separated during dicing tend to scatter easily. On the other hand, by using the adhesive tape 1 of the present embodiment having the above-described configuration, it is possible to maintain good adhesive force between the phosphor and the adhesive layer 3, and the chip scale package is individualized. It is possible to suppress the scattering of LEDs.
Further, after dicing, the adhesive layer 3 is irradiated with light such as ultraviolet rays to reduce the tacking force, so that the chip scale package LED separated from the adhesive tape 1 can be easily peeled off and the peeled chip scale is peeled off. It is possible to suppress the generation of adhesive residue on the package LED.
　続いて、実施例および比較例を用いて本発明をさらに具体的に説明する。なお、本発明は、以下の実施例に限定されるものではない。 Subsequently, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
　実施例および比較例に使用する各種の粘着剤組成物を調整するために、粘着剤組成物の主成分として下記のシリコーン系樹脂（ａ）～（ｊ）、架橋剤として下記のケイ素原子結合水素原子（ＳｉＨ）を有するオルガノポリシロキサン（オルガノハイドロジェンポリシロキサン）（ｍ）および（ｎ）を用いた。 In order to prepare various pressure-sensitive adhesive compositions used in Examples and Comparative Examples, the following silicone-based resins (a) to (j) are used as the main components of the pressure-sensitive adhesive composition, and the following silicon atom-bonded hydrogen is used as the cross-linking agent. Organopolysiloxanes (organohydrogenpolysiloxanes) (m) and (n) having an atom (SiH) were used.
　シリコーン系樹脂（ａ）～（ｄ）は、いずれもケイ素原子結合アルケニル基を含有するシリコーンガム（Ｇalk）とシリコーンレジン（Ｒ）との混合物であり、その混合比率およびケイ素原子結合アルケニル基含有量が互いに異なる。該シリコーンガム（Ｇalk）には、重量平均分子量（Ｍｗ）が約５０万の分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体を用い、該シリコーンレジン（Ｒ）には、重量平均分子量（Ｍｗ）が約５，０００のＲ2 3ＳｉＯ0.5単位（Ｍ単位）およびＳｉＯ2単位（Ｑ単位）を有するオルガノポリシロキサン（ＭＱレジン）を用いた。 The silicone-based resins (a) to (d) are all a mixture of a silicone gum (Galk ) containing a silicon atom-bonded alkenyl group and a silicone resin (R), and the mixing ratio thereof and the silicon atom-bonded alkenyl group are contained. The amounts are different from each other. For the silicone gum ( Galk ), a dimethylvinylsiloxy group-blocking dimethylsiloxane / methylvinylsiloxane copolymer having a weight average molecular weight (Mw) of about 500,000 at both ends of the molecular chain was used, and for the silicone resin (R). , Organopolysiloxane (MQ resin) having R 2 3 SiO 0.5 unit (M unit) and SiO 2 unit (Q unit) having a weight average molecular weight (Mw) of about 5,000 was used.
　また、シリコーン系樹脂（ｅ）および（ｆ）は、ともにケイ素原子結合アルケニル基を含有するシリコーンガム（Ｇalk）の単独物であり、ケイ素原子結合アルケニル基含有量が互いに異なる。シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）には、重量平均分子量（Ｍｗ）が約３０万の分子鎖両末端ジメチルヘキセニルシロキシ基封鎖ジメチルシロキサン・メチルヘキセニルシロキサン共重合体を用い、シリコーン系樹脂（ｆ）のシリコーンガム（Ｇalk）には、重量平均分子量（Ｍｗ）が約２０万の分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン重合体を用いた。 Further, the silicone-based resins (e) and (f) are both single products of the silicone gum (Galk ) containing a silicon atom-bonded alkenyl group, and the silicon atom-bonded alkenyl group contents are different from each other. For the silicone gum (Galk ) of the silicone-based resin (e), a dimethylsiloxane / methylhexenylsiloxane copolymer having a weight average molecular weight (Mw) of about 300,000 at both ends of the molecular chain and dimethylhexenylsiloxy group-sealed is used, and the silicone-based resin (e) is silicone-based. As the silicone gum (Galk ) of the resin (f), a dimethylvinylsiloxy group-blocked dimethylsiloxane polymer having a weight average molecular weight (Mw) of about 200,000 at both ends of the molecular chain was used.
　さらに、シリコーン系樹脂（ｇ）～（ｉ）は、いずれもケイ素原子結合アルケニル基を含有しないシリコーンガム（Ｇ0）とシリコーンレジン（Ｒ）との混合物であり、混合比率が互いに異なる。該シリコーンガム（Ｇ0）には、重量平均分子量（Ｍｗ）が約５０万のジメチルシロキサン重合体を用い、該シリコーンレジン（Ｒ）には、重量平均分子量（Ｍｗ）が約５，０００のＲ2 3ＳｉＯ0.5単位（Ｍ単位）およびＳｉＯ2単位（Ｑ単位）を有するオルガノポリシロキサン（ＭＱレジン）を用いた。 Further, the silicone-based resins (g) to (i) are all a mixture of a silicone gum (G 0 ) and a silicone resin (R) that do not contain a silicon atom-bonded alkenyl group, and the mixing ratios are different from each other. A dimethylsiloxane polymer having a weight average molecular weight (Mw) of about 500,000 was used for the silicone gum (G 0 ), and R having a weight average molecular weight (Mw) of about 5,000 was used for the silicone resin (R). 2 3 Organopolysiloxane (MQ resin) having 0.5 units of SiO (M units) and 2 units of SiO (Q units) was used.
　さらにまた、シリコーン系樹脂（ｊ）は、シリコーンレジン（Ｒ）の単独物であり、該シリコーンレジン（Ｒ）には、重量平均分子量（Ｍｗ）が約５，０００のＲ2 3ＳｉＯ0.5単位（Ｍ単位）およびＳｉＯ2単位（Ｑ単位）を有するオルガノポリシロキサン（ＭＱレジン）を用いた。 Furthermore, the silicone-based resin (j) is a single substance of the silicone resin (R), and the silicone resin (R) has a weight average molecular weight (Mw) of about 5,000 in 0.5 units of R 2 3 SiO (R). Organopolysiloxane (MQ resin) having 2 units of SiO (M unit) and 2 units of SiO (Q unit) was used.
・シリコーン系樹脂（ａ）
　　シリコーンガム(Ｇalk)とシリコーンレジン(Ｒ)との混合物
　　(Ｇalk)／(Ｒ)＝４０．０質量％／６０．０質量％
　　アルケニル基（ビニル基）含有量：２．０×１０-6ｍｏｌ／ｇ -Silicone resin (a)
Mixture of silicone gum (G alk ) and silicone resin (R) (G alk ) / (R) = 40.0% by mass / 60.0% by mass
Alkenyl group (vinyl group) content: 2.0 × 10 -6 mol / g
・シリコーン系樹脂（ｂ）　
　　シリコーンガム(Ｇalk)とシリコーンレジン(Ｒ)との混合物
　　(Ｇalk)／(Ｒ)＝３５．０質量％／６５．０質量％
　　アルケニル基（ビニル基）含有量：１．８×１０-6ｍｏｌ／ｇ -Silicone resin (b)
Mixture of silicone gum (G alk ) and silicone resin (R) (G alk ) / (R) = 35.0% by mass / 65.0% by mass
Alkenyl group (vinyl group) content: 1.8 × 10 -6 mol / g
・シリコーン系樹脂（ｃ）
　　シリコーンガム(Ｇalk)とシリコーンレジン(Ｒ)との混合物
　　(Ｇalk)／(Ｒ)＝５０．０質量％／５０．０質量％
　　アルケニル基（ビニル基）含有量：２．５×１０-6ｍｏｌ／ｇ -Silicone resin (c)
Mixture of silicone gum (G alk ) and silicone resin (R) (G alk ) / (R) = 50.0% by mass / 50.0% by mass
Alkenyl group (vinyl group) content: 2.5 × 10 -6 mol / g
・シリコーン系樹脂（ｄ）
　　シリコーンガム(Ｇalk)とシリコーンレジン(Ｒ)との混合物
　　(Ｇalk)／(Ｒ)＝７０．０質量％／３０．０質量％
　　アルケニル基（ビニル基）含有量：３．５×１０-6ｍｏｌ／ｇ -Silicone resin (d)
Mixture of silicone gum (G alk ) and silicone resin (R) (G alk ) / (R) = 70.0% by mass / 30.0% by mass
Alkenyl group (vinyl group) content: 3.5 × 10 -6 mol / g
・シリコーン系樹脂（ｅ）
　　シリコーンガム(Ｇalk)単体
　　アルケニル基（ヘキセニル基）含有量：２．０×１０-4ｍｏｌ／ｇ -Silicone resin (e)
Silicone gum (G alk ) elemental alkenyl group (hexenyl group) content: 2.0 × 10 -4 mol / g
・シリコーン系樹脂（ｆ）
　　シリコーンガム(Ｇalk)単体
　　アルケニル基（ビニル基）含有量：２．７×１０-3ｍｏｌ／ｇ -Silicone resin (f)
Silicone gum (G alk ) elemental alkenyl group (vinyl group) content: 2.7 × 10 -3 mol / g
・シリコーン系樹脂（ｇ）
　　シリコーンガム(Ｇ0)とシリコーンレジン(Ｒ)との混合物
　　(Ｇ0)／(Ｒ)＝５０．０質量％／５０．０質量％
　　アルケニル基不含有 ・ Silicone resin (g)
Mixture of silicone gum (G 0 ) and silicone resin (R) (G 0 ) / (R) = 50.0% by mass / 50.0% by mass
Alkenyl group free
・シリコーン系樹脂（ｈ）
　　シリコーンガム(Ｇ0)とシリコーンレジン(Ｒ)との混合物
　　(Ｇ0)／(Ｒ)＝４０．０質量％／６０．０質量％
　　アルケニル基不含有 -Silicone resin (h)
Mixture of silicone gum (G 0 ) and silicone resin (R) (G 0 ) / (R) = 40.0% by mass / 60.0% by mass
Alkenyl group free
・シリコーン系樹脂（ｉ）
　　シリコーンガム(Ｇ0)とシリコーンレジン(Ｒ)との混合物
　　(Ｇ0)／(Ｒ)＝６０．０質量％／４０．０質量％
　　アルケニル基不含有 -Silicone resin (i)
Mixture of silicone gum (G 0 ) and silicone resin (R) (G 0 ) / (R) = 60.0% by mass / 40.0% by mass
Alkenyl group free
・シリコーン系樹脂（ｊ）
　　シリコーンレジン(Ｒ)単体
　　アルケニル基不含有 -Silicone resin (j)
Silicone resin (R) simple substance alkenyl group free
・架橋剤（ｍ）
　　オルガノハイドロジェンポリシロキサン
　　ＳｉＨ基含有量：２．０×１０-2ｍｏｌ／ｇ ・ Crosslinking agent (m)
Organohydrogenpolysiloxane SiH group content: 2.0 × 10 -2 mol / g
・架橋剤（ｎ）
　　オルガノハイドロジェンポリシロキサン
　　ＳｉＨ基含有量：２．４×１０-3ｍｏｌ／ｇ -Crosslinking agent (n)
Organohydrogenpolysiloxane SiH group content: 2.4 × 10 -3 mol / g
　なお、上記で用いたシリコーン系樹脂のアルケニル基含有量および架橋剤のＳｉＨ基含有量は、５００ＭＨｚの1Ｈ－ＮＭＲ（核磁気共鳴）スペクトルを測定することにより定量した。具体的には、上記シリコーン系樹脂の不揮発成分を、内部標準試料としてジメチルスルホキシドを含む重クロロホルムに十分に溶解させ、日本電子株式会社製ＮＭＲ装置“ＪＮＭ・ＥＣＡ５００”（製品名）を用いて1Ｈ－ＮＭＲ（核磁気共鳴）スペクトルを測定した。次いで、測定スペクトルにおける内部標準試料のジメチルスルホキシドの共鳴シグナル面積（積分値）とアルケニル基の共鳴シグナル面積（積分値）を求め、その比率から、シリコーン系樹脂１ｇ（固形分）当たりのアルケニル基の含有量を算出した。また、架橋剤のＳｉＨ基含有量についても、同様にして、1Ｈ－ＮＭＲスペクトルを測定し、測定スペクトルにおける内部標準試料のジメチルスルホキシドの共鳴シグナル面積（積分値）とＳｉＨ基の共鳴シグナル面積（積分値）を求め、その比率から、架橋剤１ｇ（固形分）当たりのＳｉＨ基の含有量を算出した。なお、架橋剤がシリコーン系樹脂に最初から内添されている場合は、その1Ｈ－ＮＭＲスペクトルからアルケニル基とＳｉＨ基の含有量を同時に算出すればよい。 The alkenyl group content of the silicone resin used above and the SiH group content of the cross-linking agent were quantified by measuring a 1 H-NMR (nuclear magnetic resonance) spectrum at 500 MHz. Specifically, the non-volatile components of the silicone-based resin, was sufficiently dissolved in deuterated chloroform containing dimethylsulfoxide as the internal standard sample, using a JEOL Ltd. NMR apparatus "JNM · ECA500" (product name) 1 The H-NMR (Nuclear Magnetic Resonance) spectrum was measured. Next, the resonance signal area (integral value) of the dimethyl sulfoxide of the internal standard sample and the resonance signal area (integral value) of the alkenyl group in the measurement spectrum were obtained, and from the ratio, the alkenyl group per 1 g (solid content) of the silicone resin was used. The content was calculated. Regarding the SiH group content of the cross-linking agent, the 1 H-NMR spectrum was measured in the same manner, and the resonance signal area (integrated value) of the dimethyl sulfoxide of the internal standard sample and the resonance signal area of the SiH group (integrated value) in the measurement spectrum were measured. The integrated value) was obtained, and the content of SiH groups per 1 g (solid content) of the cross-linking agent was calculated from the ratio. When the cross-linking agent is internally added to the silicone resin from the beginning, the contents of the alkenyl group and the SiH group may be calculated at the same time from the 1 H-NMR spectrum.
１．粘着テープの作製
（実施例１）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｅ）とシリコーン系樹脂（ｇ）とシリコーン系樹脂（ｊ）とを質量比（ｅ）／（ｇ）／（ｊ）が２．７２／８３．４３／１３．８５となるように混合したシリコーン系樹脂（Ｓ１）をトルエンにて希釈・撹拌し、シリコーン樹脂（Ｓ１）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４４．４／５５．６であり、アルケニル基含有量が５．４×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 1. 1. Preparation of Adhesive Tape (Example 1)
<Preparation of silicone resin solution>
The mass ratio (e) / (g) / (j) of the silicone-based resin (e), the silicone-based resin (g), and the silicone-based resin (j) is 2.72 / 83.43 / 13.85. The silicone resin (S1) mixed in the above was diluted with toluene and stirred to prepare a silicone resin (S1) solution (solid content concentration: 30% by mass). This silicone-based resin (S1) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 44.4 / 55.6, and has an alkenyl group content of 5. It was 4 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is the total amount of the "silicone gum (G alk ) of the silicone resin (e)" and the "silicone gum (G 0 ) of the silicone resin (g)". .. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (g)" and the "silicone resin (R) of the silicone resin (j)".
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が８．８２／９１．１８となるように混合した架橋剤（Ｃ１）をトルエンにて希釈・撹拌し、架橋剤（Ｃ１）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ１）は、ＳｉＨ基含有量が４．０×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C1) obtained by mixing the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 8.82 / 91.18 is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C1) solution (solid content concentration: 20% by mass). This cross-linking agent (C1) had a SiH group content of 4.0 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ１）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ１）溶液３．００質量部（固形分換算０．６０質量部、ＳｉＨ基／アルケニル基のモル比＝４．４）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”４．１８質量部（固形分換算１．６７質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液４．４７質量部（固形分換算０．６７質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S1) solution (100 parts by mass in terms of solid content), 3.00 parts by mass of the cross-linking agent (C1) solution (0.60 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 4.4), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 4.18 parts by mass (solid content equivalent 1.67 parts by mass, solid content concentration 40% by mass) in a disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 4.47 parts by mass (0.67 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が５８μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.
（実施例２）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｅ）とシリコーン系樹脂（ｈ）とシリコーン系樹脂（ｊ）とを質量比（ｅ）／（ｈ）／（ｊ）が１．１９／９６．９９／１．８２となるように混合したシリコーン系樹脂（Ｓ２）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ２）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ２）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）の混合比率（（Ｇ）／（Ｒ））が４０．０／６０．０であり、アルケニル基含有量が２．４×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｈ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｈ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 (Example 2)
<Preparation of silicone resin solution>
The mass ratio (e) / (h) / (j) of the silicone-based resin (e), the silicone-based resin (h), and the silicone-based resin (j) is 1.19 / 96.99 / 1.82. The silicone-based resin (S2) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S2) solution (solid content concentration: 30% by mass). This silicone-based resin (S2) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 40.0 / 60.0, and has an alkenyl group content of 2. It was 4 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is the total amount of the "silicone gum (G alk ) of the silicone resin (e)" and the "silicone gum (G 0 ) of the silicone resin (h)". .. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (h)" and the "silicone resin (R) of the silicone resin (j)".
　＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が２．８３／９７．１７となるように混合した架橋剤（Ｃ２）をトルエンにて希釈・撹拌し、架橋剤（Ｃ２）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ２）は、ＳｉＨ基含有量が２．９×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C2), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 2.83 / 97.17, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C2) solution (solid content concentration: 20% by mass). This cross-linking agent (C2) had a SiH group content of 2.9 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ２）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ２）溶液４．１０質量部（固形分換算０．８２質量部、ＳｉＨ基／アルケニル基のモル比＝１０．０）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”３．８５質量部（固形分換算１．５４質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液６．４７質量部（固形分換算０．９７質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S2) solution (100 parts by mass in terms of solid content), 4.10 parts by mass of the cross-linking agent (C2) solution (0.82 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 10.0), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 3.85 parts by mass (solid content equivalent 1.54 parts by mass, solid content concentration 40% by mass) in a disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 6.47 parts by mass (0.97 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ１２μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが１０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が２２μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 12 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 10 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 22 μm after drying was obtained.
（実施例３）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｅ)とシリコーン系樹脂（ｇ）とシリコーン系樹脂（ｊ）とを質量比（ｅ）／（ｇ）／（ｊ）が２．０９／８７．２６／１０．６５となるように混合したシリコーン系樹脂（Ｓ３）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ３）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ３）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４５．７／５４．３であり、アルケニル基含有量が４．２×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 (Example 3)
<Preparation of silicone resin solution>
The mass ratio (e) / (g) / (j) of the silicone-based resin (e), the silicone-based resin (g), and the silicone-based resin (j) is 2.09 / 87.26 / 10.65. The silicone-based resin (S3) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S3) solution (solid content concentration: 30% by mass). This silicone-based resin (S3) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 45.7 / 54.3, and has an alkenyl group content of 4. It was 2 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is the total amount of the "silicone gum (G alk ) of the silicone resin (e)" and the "silicone gum (G 0 ) of the silicone resin (g)". .. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (g)" and the "silicone resin (R) of the silicone resin (j)".
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が９．６３／９０．３７となるように混合した架橋剤（Ｃ３）をトルエンにて希釈・撹拌し、架橋剤（Ｃ３）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ３）は、ＳｉＨ基含有量が４．１×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C3), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 9.63 / 90.37, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C3) solution (solid content concentration: 20% by mass). This cross-linking agent (C3) had a SiH group content of 4.1 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ３）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ３）溶液２．１０質量部（固形分換算０．４２質量部、ＳｉＨ基／アルケニル基のモル比＝４．２）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”４．３８質量部（固形分換算１．７５質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液３．１３質量部（固形分換算０．４７質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S3) solution (100 parts by mass in terms of solid content), 2.10 parts by mass of the cross-linking agent (C3) solution (0.42 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 4.2), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 4.38 parts by mass (solid content equivalent 1.75 parts by mass, solid content concentration 40% by mass) to a disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 3.13 parts by mass (0.47 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが４０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が９０μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 50 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 40 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 90 μm after drying was obtained.
（実施例４）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｂ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｇ）とを質量比（ｂ）／（ｅ）／（ｇ）が４９．５１／０．９７／４９．５２となるように混合したシリコーン系樹脂（Ｓ４）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ４）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ４）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４３．１／５６．９であり、アルケニル基含有量が２．８×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンガム（Ｇalk）」とシリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」との合計量である。 (Example 4)
<Preparation of silicone resin solution>
The mass ratio (b) / (e) / (g) of the silicone-based resin (b), the silicone-based resin (e), and the silicone-based resin (g) is 49.51 / 0.97 / 49.52. The silicone-based resin (S4) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S4) solution (solid content concentration: 30% by mass). This silicone-based resin (S4) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 43.1 / 56.9, and has an alkenyl group content of 2. It was .8 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", "silicone gum (G alk)" of the silicone resin (e), and "silicone resin (g alk)". ) Silicone gum (G 0 ) ”. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (b)" and the "silicone resin (R) of the silicone resin (g)".
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が５．５０／９４．５０となるように混合した架橋剤（Ｃ４）をトルエンにて希釈・撹拌し、架橋剤（Ｃ４）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ４）は、ＳｉＨ基含有量が３．４×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C4), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 5.50 / 94.50, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C4) solution (solid content concentration: 20% by mass). This cross-linking agent (C4) had a SiH group content of 3.4 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ４）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ４）溶液１．７５質量部（固形分換算０．３５質量部、ＳｉＨ基／アルケニル基のモル比＝４．１）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”２．４８質量部（固形分換算０．９９質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液２．６７質量部（固形分換算０．４０質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S4) solution (100 parts by mass in terms of solid content), 1.75 parts by mass of the cross-linking agent (C4) solution (0.35 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 4.1), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 2.48 parts by mass (solid content equivalent 0.99 parts by mass, solid content concentration 40% by mass) in a disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 2.67 parts by mass (0.40 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ１２５μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が１４５μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 125 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 145 μm after drying was obtained.
（実施例５）
　シリコーン系樹脂（Ｓ５）溶液を下記のように調製し、粘着剤溶液の作製において、シリコーン系樹脂（Ｓ４）溶液をシリコーン系樹脂（Ｓ５）溶液に変更し、架橋剤（Ｃ４）溶液の配合量を２．１０質量部（固形分換算０．４２質量部、ＳｉＨ基／アルケニル基のモル比＝４．１）、有機過酸化物溶液の配合量を１．９３質量部（固形分換算０．７７質量部）、光感応白金（Ｐｔ）触媒の溶液の配合量を３．２０質量部（固形分換算０．４８質量部）に変更し、粘着剤層３の乾燥後の厚さを３８μｍに変更した以外は、実施例４と同様にして乾燥後の総厚が５８μｍの粘着テープ１を得た。 (Example 5)
The silicone-based resin (S5) solution was prepared as follows, and in the preparation of the pressure-sensitive adhesive solution, the silicone-based resin (S4) solution was changed to the silicone-based resin (S5) solution, and the blending amount of the cross-linking agent (C4) solution was changed. 2.10 parts by mass (0.42 parts by mass in terms of solid content, molar ratio of SiH group / alkenyl group = 4.1), and the blending amount of the organic peroxide solution was 1.93 parts by mass in terms of solid content (0. 77 parts by mass), the blending amount of the photosensitive platinum (Pt) catalyst solution was changed to 3.20 parts by mass (0.48 parts by mass in terms of solid content), and the thickness of the pressure-sensitive adhesive layer 3 after drying was 38 μm. An adhesive tape 1 having a total thickness of 58 μm after drying was obtained in the same manner as in Example 4 except for the modification.
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｂ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｇ）とを質量比（ｂ）／（ｅ）／（ｇ）が６０．３７／１．１８／３８．４５となるように混合したシリコーン系樹脂（Ｓ５）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ５）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ５）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４１．５／５８．５であり、アルケニル基含有量が３．４×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」との合計量である。 <Preparation of silicone resin solution>
The mass ratio (b) / (e) / (g) of the silicone-based resin (b), the silicone-based resin (e), and the silicone-based resin (g) is 60.37 / 1.18 / 38.45. The silicone-based resin (S5) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S5) solution (solid content concentration: 30% by mass). This silicone-based resin (S5) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 41.5 / 58.5, and has an alkenyl group content of 3. It was 4 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". g) is the total amount of silicone gum (G 0) ”. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (b)" and the "silicone resin (R) of the silicone resin (g)".
（実施例６）
　シリコーン系樹脂（Ｓ６）溶液を下記のように調製し、粘着剤溶液の作製において、シリコーン系樹脂（Ｓ５）溶液をシリコーン系樹脂（Ｓ６）溶液に変更し、架橋剤（Ｃ４）溶液の配合量を１．４０質量部（固形分換算０．２８質量部、ＳｉＨ基／アルケニル基のモル比＝４．１）、有機過酸化物溶液の配合量を２．９８質量部（固形分換算１．１９質量部）、光感応白金（Ｐｔ）触媒の溶液の配合量を２．１３質量部（固形分換算０．３２質量部）に変更した以外は、実施例５と同様にして乾燥後の総厚が５８μｍの粘着テープ１を得た。 (Example 6)
The silicone-based resin (S6) solution was prepared as follows, and in the preparation of the pressure-sensitive adhesive solution, the silicone-based resin (S5) solution was changed to the silicone-based resin (S6) solution, and the blending amount of the cross-linking agent (C4) solution was changed. 1.40 parts by mass (0.28 parts by mass in terms of solid content, molar ratio of SiH group / alkenyl group = 4.1), and 2.98 parts by mass of organic peroxide solution (in terms of solid content 1. 19 parts by mass), the total amount after drying was the same as in Example 5, except that the blending amount of the photosensitive platinum (Pt) catalyst solution was changed to 2.13 parts by mass (0.32 parts by mass in terms of solid content). An adhesive tape 1 having a thickness of 58 μm was obtained.
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｂ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｇ）とを質量比（ｂ）／（ｅ）／（ｇ）が３９．６９／０．７８／５９．５３となるように混合したシリコーン系樹脂（Ｓ６）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ６）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ６）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４４．４／５５．６であり、アルケニル基含有量が２．３×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」との合計量である。 <Preparation of silicone resin solution>
The mass ratio (b) / (e) / (g) of the silicone-based resin (b), the silicone-based resin (e), and the silicone-based resin (g) is 39.69 / 0.78 / 59.53. The silicone-based resin (S6) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S6) solution (solid content concentration: 30% by mass). This silicone-based resin (S6) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 44.4 / 55.6, and has an alkenyl group content of 2. It was 3 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". g) is the total amount of silicone gum (G 0) ”. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (b)" and the "silicone resin (R) of the silicone resin (g)".
（実施例７）
　シリコーン系樹脂（Ｓ７）溶液を下記のように調製し、粘着剤溶液の作製において、シリコーン系樹脂（Ｓ５）溶液をシリコーン系樹脂（Ｓ７）溶液に変更し、架橋剤（Ｃ４）溶液の配合量を１．７５質量部（固形分換算０．３５質量部、ＳｉＨ基／アルケニル基のモル比＝４．０）、有機過酸化物溶液の配合量を２．４８質量部（固形分換算０．９９質量部）、光感応白金（Ｐｔ）触媒の溶液の配合量を２．６７質量部（固形分換算０．４０質量部）に変更した以外は、実施例５と同様にして乾燥後の総厚が５８μｍの粘着テープ１を得た。 (Example 7)
The silicone-based resin (S7) solution was prepared as follows, and in the preparation of the pressure-sensitive adhesive solution, the silicone-based resin (S5) solution was changed to the silicone-based resin (S7) solution, and the blending amount of the cross-linking agent (C4) solution was changed. 1.75 parts by mass (0.35 parts by mass in terms of solid content, molar ratio of SiH group / alkenyl group = 4.0), and 2.48 parts by mass of organic peroxide solution (0.0 by mass in terms of solid content). 99 parts by mass), and the total amount after drying was the same as in Example 5, except that the blending amount of the photosensitive platinum (Pt) catalyst solution was changed to 2.67 parts by mass (0.40 parts by mass in terms of solid content). An adhesive tape 1 having a thickness of 58 μm was obtained.
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ａ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｇ）とを質量比（ａ）／（ｅ）／（ｇ）が４９．５１／０．９８／４９．５１となるように混合したシリコーン系樹脂（Ｓ７）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ７）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ７）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４５．５／５４．５であり、アルケニル基含有量が２．９×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ａ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ａ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」との合計量である。 <Preparation of silicone resin solution>
The mass ratio (a) / (e) / (g) of the silicone-based resin (a), the silicone-based resin (e), and the silicone-based resin (g) is 49.51 / 0.98 / 49.51. The silicone-based resin (S7) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S7) solution (solid content concentration: 30% by mass). This silicone-based resin (S7) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 45.5 / 54.5, and has an alkenyl group content of 2. It was .9 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (a)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". g) Silicone gum (G 0 ) ”is the total amount. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (a)" and the "silicone resin (R) of the silicone resin (g)".
（実施例８）
　シリコーン系樹脂（Ｓ８）溶液を下記のように調製し、粘着剤溶液の作製において、シリコーン系樹脂（Ｓ５）溶液をシリコーン系樹脂（Ｓ８）溶液に変更し、架橋剤（Ｃ４）溶液の配合量を１．４０質量部（固形分換算０．２８質量部、ＳｉＨ基／アルケニル基のモル比＝３．７）、有機過酸化物溶液の配合量を２．９５質量部（固形分換算１．１８質量部）、光感応白金（Ｐｔ）触媒の溶液の配合量を２．１３質量部（固形分換算０．３２質量部）に変更した以外は、実施例５と同様にして乾燥後の総厚が５８μｍの粘着テープ１を得た。 (Example 8)
The silicone-based resin (S8) solution was prepared as follows, and in the preparation of the adhesive solution, the silicone-based resin (S5) solution was changed to the silicone-based resin (S8) solution, and the blending amount of the cross-linking agent (C4) solution was changed. 1.40 parts by mass (0.28 parts by mass in terms of solid content, molar ratio of SiH group / alkenyl group = 3.7), and 2.95 parts by mass of organic peroxide solution (in terms of solid content 1. 18 parts by mass), and the total amount after drying was the same as in Example 5, except that the blending amount of the photosensitive platinum (Pt) catalyst solution was changed to 2.13 parts by mass (0.32 parts by mass in terms of solid content). An adhesive tape 1 having a thickness of 58 μm was obtained.
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｃ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｈ）とシリコーン系樹脂（ｊ）とを質量比（ｃ）／（ｅ）／（ｈ）／（ｊ）が３９．４６／０．７７／５９．１８／０．５９となるように混合したシリコーン系樹脂（Ｓ８）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ８）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ８）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が５６．０／４４．０であり、アルケニル基含有量が２．５×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｃ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｈ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｃ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｈ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 <Preparation of silicone resin solution>
The mass ratio (c) / (e) / (h) / (j) of the silicone-based resin (c), the silicone-based resin (e), the silicone-based resin (h), and the silicone-based resin (j) is 39.46. The silicone resin (S8) mixed so as to be /0.77 / 59.18 / 0.59 is diluted and stirred with toluene to prepare a silicone resin (S8) solution (solid content concentration: 30% by mass). did. This silicone-based resin (S8) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 56.0 / 44.0 and an alkenyl group content of 2. It was .5 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (c)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". h) is the total amount of silicone gum (G 0) ”. The total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (c)", "silicone resin (R) of silicone resin (h)" and "silicone resin (j)". It is the total amount with "silicone resin (R)".
（実施例９）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｂ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂(ｇ)とシリコーン系樹脂（ｊ）とを質量比（ｂ）／（ｅ）／（ｇ）／（ｊ）が３３．１４／０．０７／６６．２９／０．５０となるように混合したシリコーン系樹脂（Ｓ９）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ９）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ９）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４４．８／５５．２であり、アルケニル基含有量が７．１×１０-7ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 (Example 9)
<Preparation of silicone resin solution>
The mass ratio (b) / (e) / (g) / (j) of the silicone-based resin (b), the silicone-based resin (e), the silicone-based resin (g), and the silicone-based resin (j) is 33.14. The silicone-based resin (S9) mixed so as to be /0.07 / 66.29 / 0.50 is diluted and stirred with toluene to prepare a silicone-based resin (S9) solution (solid content concentration: 30% by mass). did. This silicone-based resin (S9) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 44.8 / 55.2, and has an alkenyl group content of 7. It was 1 × 10 -7 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". g) is the total amount of silicone gum (G 0) ”. The total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (b)", "silicone resin (R) of silicone resin (g)" and "silicone resin (j)". It is the total amount with "silicone resin (R)".
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が０．５８／９９．４２となるように混合した架橋剤（Ｃ５）をトルエンにて希釈・撹拌し、架橋剤（Ｃ５）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ５）は、ＳｉＨ基含有量が２．５×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C5), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 0.58 / 99.42, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C5) solution (solid content concentration: 20% by mass). This cross-linking agent (C5) had a SiH group content of 2.5 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ９）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ５）溶液１．１０質量部（固形分換算０．２２質量部、ＳｉＨ基／アルケニル基のモル比＝７．８）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”２．９０質量部（固形分換算１．１６質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液１．８０質量部（固形分換算０．２７質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S9) solution (100 parts by mass in terms of solid content), 1.10 parts by mass of the cross-linking agent (C5) solution (0.22 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 7.8), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 2.90 parts by mass (solid content equivalent 1.16 parts by mass, solid content concentration 40% by mass) to the disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 1.80 parts by mass (0.27 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２５μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が６３μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 25 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 63 μm after drying was obtained.
（実施例１０）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｃ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂(ｇ)とシリコーン系樹脂(ｊ)とを質量比（ｃ）／（ｅ）／（ｇ）／（ｊ）が４８．９１／１．４５／４８．９１／０．７３となるように混合したシリコーン系樹脂（Ｓ１０）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ１０）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１０）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が５０．４／４９．６であり、アルケニル基含有量が４．１×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｃ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｃ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 (Example 10)
<Preparation of silicone resin solution>
The mass ratio (c) / (e) / (g) / (j) of the silicone-based resin (c), the silicone-based resin (e), the silicone-based resin (g), and the silicone-based resin (j) is 48.91. A silicone resin (S10) mixed so as to be /1.45 / 48.91 / 0.73 is diluted and stirred with toluene to prepare a silicone resin (S10) solution (solid content concentration: 30% by mass). did. This silicone-based resin (S10) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 50.4 / 49.6, and has an alkenyl group content of 4. It was 1 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (c)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". g) Silicone gum (G 0 ) ”is the total amount. The total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (c)", "silicone resin (R) of silicone resin (g)" and "silicone resin (j)". It is the total amount with "silicone resin (R)".
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が８．０４／９１．９となるように混合した架橋剤（Ｃ６）をトルエンにて希釈・撹拌し、架橋剤（Ｃ６）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ６）は、ＳｉＨ基含有量が３．８×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C6), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 8.04 / 91.9, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C6) solution (solid content concentration: 20% by mass). This cross-linking agent (C6) had a SiH group content of 3.8 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ１０）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ６）溶液１．７５質量部（固形分換算０．３５質量部、ＳｉＨ基／アルケニル基のモル比＝３．３）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”１．８３質量部（固形分換算０．７３質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液２．６０質量部（固形分換算０．３９質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S10) solution (100 parts by mass in terms of solid content), 1.75 parts by mass of the cross-linking agent (C6) solution (0.35 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 3.3), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 1.83 parts by mass (solid content equivalent 0.73 parts by mass, solid content concentration 40% by mass) in a disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 2.60 parts by mass (0.39 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が５８μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.
（比較例１）
　シリコーン系樹脂（Ｓ１１）溶液を下記のように調製し、シリコーン系樹脂（Ｓ１）溶液をシリコーン系樹脂（Ｓ１１）溶液に変更し、粘着剤溶液の作製において、架橋剤および有機過酸化物を配合せずに、光感応白金（Ｐｔ）触媒の溶液の配合量を５．３３質量部（固形分換算０．８０質量部）に変更し、粘着剤層３の乾燥後の厚さを３５μｍに変更した以外は、実施例１と同様にして乾燥後の総厚が７３μｍの粘着テープ１を得た。 (Comparative Example 1)
The silicone-based resin (S11) solution was prepared as follows, the silicone-based resin (S1) solution was changed to the silicone-based resin (S11) solution, and a cross-linking agent and an organic peroxide were added in the preparation of the pressure-sensitive adhesive solution. Instead, the amount of the solution of the photosensitive platinum (Pt) catalyst was changed to 5.33 parts by mass (0.80 parts by mass in terms of solid content), and the thickness of the pressure-sensitive adhesive layer 3 after drying was changed to 35 μm. An adhesive tape 1 having a total thickness of 73 μm after drying was obtained in the same manner as in Example 1.
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ａ）とシリコーン系樹脂（ｆ）とを質量比（ａ）／（ｆ）が９９．９０／０．１０となるように混合したシリコーン系樹脂（Ｓ１１）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ１１）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１１）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４０．１／５９．９であり、アルケニル基含有量が４．７×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ａ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｆ）のシリコーンガム（Ｇalk）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、シリコーン系樹脂（ａ）のシリコーンレジン（Ｒ）の量である。 <Preparation of silicone resin solution>
The silicone resin (S11), which is a mixture of the silicone resin (a) and the silicone resin (f) so that the mass ratio (a) / (f) is 99.90 / 0.10, is diluted with toluene. The mixture was stirred to prepare a silicone resin (S11) solution (solid content concentration: 30% by mass). This silicone-based resin (S11) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 40.1 / 59.9, and has an alkenyl group content of 4. It was 7 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is the total amount of the "silicone gum (G alk ) of the silicone resin (a)" and the "silicone gum (G alk ) of the silicone resin (f)". .. The total mass of the silicone resin (R) is the amount of the silicone resin (R) of the silicone resin (a).
（比較例２）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｂ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｇ）とを質量比（ｂ）／（ｅ）／（ｇ）が４９．２８／１．４５／４９．２８となるように混合したシリコーン系樹脂（Ｓ１２）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ１２）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１２）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４３．３／５６．７であり、アルケニル基含有量が３．８×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｇ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｇ）のシリコーンレジン（Ｒ）」との合計量である。 (Comparative Example 2)
<Preparation of silicone resin solution>
The mass ratio (b) / (e) / (g) of the silicone-based resin (b), the silicone-based resin (e), and the silicone-based resin (g) is 49.28 / 1.45 / 49.28. The silicone-based resin (S12) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S12) solution (solid content concentration: 30% by mass). This silicone-based resin (S12) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 43.3 / 56.7, and has an alkenyl group content of 3. It was .8 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". g) is the total amount of silicone gum (G 0) ”. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (b)" and the "silicone resin (R) of the silicone resin (g)".
＜架橋剤溶液の調製＞
　続いて、実施例１０と同様にして、架橋剤（Ｃ６）溶液（固形分濃度２０質量％）を調製した。 <Preparation of cross-linking agent solution>
Subsequently, a cross-linking agent (C6) solution (solid content concentration 20% by mass) was prepared in the same manner as in Example 10.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ１２）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ６）溶液１．７５質量部（固形分換算０．３５質量部、ＳｉＨ基／アルケニル基のモル比＝３．６）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”２．４８質量部（固形分換算０．９９質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、ダウ・東レ株式会社製白金（Ｐｔ）金属系触媒“ＮＣ－２５”（商品名、固形分濃度２５質量％）の溶液２．９６質量部（固形分換算０．７４質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S12) solution (100 parts by mass in terms of solid content), 1.75 parts by mass of the cross-linking agent (C6) solution (0.35 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 3.6), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 2.48 parts by mass (solid content equivalent 0.99 parts by mass, solid content concentration 40% by mass) to the disper Then, the solution of platinum (Pt) metal catalyst "NC-25" (trade name, solid content concentration 25% by mass) manufactured by Dow Toray Co., Ltd. was 2.96 parts by mass (2% by mass). 0.74 parts by mass in terms of solid content) was blended with a disper, and the mixture was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が５８μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.
（比較例３）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｅ）とシリコーン系樹脂（ｈ）とを質量比（ｅ）／（ｈ）が０．２６／９９．７４となるように混合したシリコーン系樹脂（Ｓ１３）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ１３）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１３）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が４０．２／５９．８であり、アルケニル基含有量が５．２×１０-7ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｈ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、シリコーン系樹脂（ｈ）のシリコーンレジン（Ｒ）の量である。 (Comparative Example 3)
<Preparation of silicone resin solution>
The silicone resin (S13), which is a mixture of the silicone resin (e) and the silicone resin (h) so that the mass ratio (e) / (h) is 0.26 / 99.74, is diluted with toluene. The mixture was stirred to prepare a silicone resin (S13) solution (solid content concentration: 30% by mass). This silicone-based resin (S13) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 40.2 / 59.8, and has an alkenyl group content of 5. It was 2 × 10 -7 mol / g. Here, the total mass of the silicone gum (G) is the total amount of the "silicone gum (G alk ) of the silicone resin (e)" and the "silicone gum (G 0 ) of the silicone resin (h)". .. The total mass of the silicone resin (R) is the amount of the silicone resin (R) of the silicone resin (h).
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が１．１５／９８．８５となるように混合した架橋剤（Ｃ７）をトルエンにて希釈・撹拌し、架橋剤（Ｃ７）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ７）は、ＳｉＨ基含有量が２．６×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C7), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 1.15 / 98.85, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C7) solution (solid content concentration: 20% by mass). This cross-linking agent (C7) had a SiH group content of 2.6 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ１３）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ７）溶液２．２０質量部（固形分換算０．４４質量部、ＳｉＨ基／アルケニル基のモル比＝２２．２）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”４．９８質量部（固形分換算１．９９質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液３．５３質量部（固形分換算０．５３質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S13) solution (100 parts by mass in terms of solid content), 2.20 parts by mass of the cross-linking agent (C7) solution (0.44 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 22.2), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Nipper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 4.98 parts by mass (solid content equivalent 1.99 parts by mass, solid content concentration 40% by mass) to a disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 3.53 parts by mass (0.53 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が５８μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.
（比較例４）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｅ）とシリコーン系樹脂（ｉ）とシリコーン系樹脂（ｊ）とを質量比（ｅ）／（ｉ）／（ｊ）が４．６７／７９．４４／１５．８９となるように混合したシリコーン系樹脂（Ｓ１４）をトルエンにて希釈・撹拌し、シリコーン樹脂（Ｓ１４）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１４）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が５２．３／４７．７であり、アルケニル基含有量が９．４×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｉ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｉ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 (Comparative Example 4)
<Preparation of silicone resin solution>
The mass ratio (e) / (i) / (j) of the silicone-based resin (e), the silicone-based resin (i), and the silicone-based resin (j) is 4.67 / 79.44 / 15.89. The silicone resin (S14) mixed in the above was diluted with toluene and stirred to prepare a silicone resin (S14) solution (solid content concentration: 30% by mass). This silicone-based resin (S14) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 52.3 / 47.7, and has an alkenyl group content of 9. It was 4 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is the total amount of the "silicone gum (G alk ) of the silicone resin (e)" and the "silicone gum (G 0 ) of the silicone resin (i)". .. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (i)" and the "silicone resin (R) of the silicone resin (j)".
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が１４．８８／８５．１２となるように混合した架橋剤（Ｃ８）をトルエンにて希釈・撹拌し、架橋剤（Ｃ８）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ８）は、ＳｉＨ基含有量が５．０×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C8), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 14.88 / 85.12, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C8) solution (solid content concentration: 20% by mass). This cross-linking agent (C8) had a SiH group content of 5.0 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ１４）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ８）溶液３．１０質量部（固形分換算０．６２質量部、ＳｉＨ基／アルケニル基のモル比＝３．３）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”１．２０質量部（固形分換算０．４８質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、シグマ アルドリッチ ジャパン合同会社製の光感応白金（Ｐｔ）触媒“トリメチル（メチルシクロペンタジエニル）白金（ＩＶ）”をトルエンで固形分濃度１５質量％に希釈した溶液４．２７質量部（固形分換算０．６４質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S14) solution (100 parts by mass in terms of solid content), 3.10 parts by mass of the cross-linking agent (C8) solution (0.62 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 3.3), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 1.20 parts by mass (solid content equivalent 0.48 parts by mass, solid content concentration 40% by mass) in a disper Then, the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma Aldrich Japan LLC was mixed with toluene to a solid content concentration of 15% by mass. 4.27 parts by mass (0.64 parts by mass in terms of solid content) of the diluted solution was mixed with a disper, and the solution was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が５８μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.
（比較例５）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｂ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｈ）とシリコーン系樹脂（ｊ）とを質量比（ｂ）／（ｅ）／（ｈ）／（ｊ）が４７．２９／０．６９／４７．２９／４．７３となるように混合したシリコーン系樹脂（Ｓ１５）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ１５）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１５）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が３６．２／６３．８であり、アルケニル基含有量が２．３×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｈ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｂ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｈ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｊ）のシリコーンレジン（Ｒ）」との合計量である。 (Comparative Example 5)
<Preparation of silicone resin solution>
The mass ratio (b) / (e) / (h) / (j) of the silicone-based resin (b), the silicone-based resin (e), the silicone-based resin (h), and the silicone-based resin (j) is 47.29. The silicone resin (S15) mixed so as to be /0.69 / 47.29 / 4.73 is diluted and stirred with toluene to prepare a silicone resin (S15) solution (solid content concentration: 30% by mass). did. This silicone-based resin (S15) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 36.2 / 63.8, and has an alkenyl group content of 2. It was 3 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (b)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". h) is the total amount of silicone gum (G 0) ”. The total mass of the silicone resin (R) is that of "silicone resin (R) of silicone resin (b)", "silicone resin (R) of silicone resin (h)" and "silicone resin (j)". It is the total amount with "silicone resin (R)".
＜架橋剤溶液の調製＞
　続いて、架橋剤（ｍ）と架橋剤（ｎ）とを質量比（ｍ）／（ｎ）が４．１９／９５．８１となるように混合した架橋剤（Ｃ９）をトルエンにて希釈・撹拌し、架橋剤（Ｃ９）溶液（固形分濃度２０質量％）を調製した。この架橋剤（Ｃ９）は、ＳｉＨ基含有量が３．１×１０-3ｍｏｌ／ｇであった。 <Preparation of cross-linking agent solution>
Subsequently, the cross-linking agent (C9), which is a mixture of the cross-linking agent (m) and the cross-linking agent (n) so that the mass ratio (m) / (n) is 4.19 / 95.81, is diluted with toluene. The mixture was stirred to prepare a cross-linking agent (C9) solution (solid content concentration: 20% by mass). This cross-linking agent (C9) had a SiH group content of 3.1 × 10 -3 mol / g.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ１５）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ９）溶液１．６５質量部（固形分換算０．３３質量部、ＳｉＨ基／アルケニル基のモル比＝４．４）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”２．３８質量部（固形分換算０．９５質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、ダウ・東レ株式会社製白金（Ｐｔ）金属系触媒“ＮＣ－２５”（商品名、固形分濃度２５質量％）の溶液２．５３質量部（固形分換算０．３８質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S15) solution (100 parts by mass in terms of solid content), 1.65 parts by mass of the cross-linking agent (C9) solution (0.33 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 4.4), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 2.38 parts by mass (solid content equivalent 0.95 parts by mass, solid content concentration 40% by mass) in a disper Then, the solution was uniformly stirred and mixed. Next, 2.53 parts by mass (trade name, solid content concentration 25% by mass) of a platinum (Pt) metal catalyst "NC-25" (trade name, solid content concentration 25% by mass) manufactured by Dow Toray Co., Ltd. ( A solid content equivalent of 0.38 parts by mass) was blended with a disper, and the mixture was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが３０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が６８μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 30 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 68 μm after drying was obtained.
（比較例６）
＜シリコーン系樹脂溶液の調製＞
　シリコーン系樹脂（ｄ）とシリコーン系樹脂（ｅ）とシリコーン系樹脂（ｉ）とを質量比（ｄ）／（ｅ）／（ｉ）が４９．２８／１．４５／４９．２８となるように混合したシリコーン系樹脂（Ｓ１６）をトルエンにて希釈・撹拌し、シリコーン系樹脂（Ｓ１６）溶液（固形分濃度３０質量％）を調製した。このシリコーン系樹脂（Ｓ１６）は、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が６５．５／３４．５であり、アルケニル基含有量が４．６×１０-6ｍｏｌ／ｇであった。ここで、シリコーンガム（Ｇ）の総質量は、「シリコーン系樹脂（ｄ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｅ）のシリコーンガム（Ｇalk）」と「シリコーン系樹脂（ｉ）のシリコーンガム（Ｇ0）」との合計量である。また、シリコーンレジン（Ｒ）の総質量は、「シリコーン系樹脂（ｄ）のシリコーンレジン（Ｒ）」と「シリコーン系樹脂（ｉ）のシリコーンレジン（Ｒ）」との合計量である。 (Comparative Example 6)
<Preparation of silicone resin solution>
The mass ratio (d) / (e) / (i) of the silicone-based resin (d), the silicone-based resin (e), and the silicone-based resin (i) is 49.28 / 1.45 / 49.28. The silicone-based resin (S16) mixed in the above was diluted with toluene and stirred to prepare a silicone-based resin (S16) solution (solid content concentration: 30% by mass). This silicone-based resin (S16) has a mixing ratio ((G) / (R)) of silicone gum (G) and silicone resin (R) of 65.5 / 34.5, and has an alkenyl group content of 4. It was .6 × 10 -6 mol / g. Here, the total mass of the silicone gum (G) is "silicone gum (G alk ) of the silicone resin (d)", "silicone gum (G alk ) of the silicone resin (e)", and "silicone resin (G alk)". i) Silicone gum (G 0 ) ”is the total amount. The total mass of the silicone resin (R) is the total amount of the "silicone resin (R) of the silicone resin (d)" and the "silicone resin (R) of the silicone resin (i)".
＜架橋剤溶液の調製＞
　続いて、実施例１０と同様にして、架橋剤（Ｃ６）溶液（固形分濃度２０質量％）を調製した。 <Preparation of cross-linking agent solution>
Subsequently, a cross-linking agent (C6) solution (solid content concentration 20% by mass) was prepared in the same manner as in Example 10.
＜粘着剤溶液の作製＞
　続いて、上記シリコーン系樹脂（Ｓ１６）溶液３３３．００質量部（固形分換算１００質量部）に対して、架橋剤（Ｃ６）溶液１．７５質量部（固形分換算０．３５質量部、ＳｉＨ基／アルケニル基のモル比＝２．９）、日油株式会社製の有機過酸化物［（ジ－（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイドの混合物］溶液“ナイパーＢＭＴ－４０Ｋ（商品名、１分間半減期温度：１３１．１℃）”２．４８質量部（固形分換算０．９９質量部、固形分濃度４０質量％）をディスパーにて配合し、均一に撹拌・混合した。次いで、ダウ・東レ株式会社製白金（Ｐｔ）金属系触媒“ＮＣ－２５”（商品名、固形分濃度２５質量％）の溶液２．６０質量部（固形分換算０．３９質量部）をディスパーにて配合し、均一に撹拌・混合して塗工用粘着剤溶液を作製した。 <Preparation of adhesive solution>
Subsequently, with respect to 333.00 parts by mass of the silicone resin (S16) solution (100 parts by mass in terms of solid content), 1.75 parts by mass of the cross-linking agent (C6) solution (0.35 parts by mass in terms of solid content, SiH). Group / alkenyl group molar ratio = 2.9), organic peroxide manufactured by Nichiyu Co., Ltd. [(di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Mixture of] Solution "Niper BMT-40K (trade name, 1 minute half-life temperature: 131.1 ° C.)" 2.48 parts by mass (solid content equivalent 0.99 parts by mass, solid content concentration 40% by mass) in a disper Then, the solution of platinum (Pt) metal catalyst "NC-25" (trade name, solid content concentration 25% by mass) manufactured by Dow Toray Co., Ltd. was 2.60 parts by mass (2% by mass). A solid content equivalent of 0.39 parts by mass) was blended with a disper, and the mixture was uniformly stirred and mixed to prepare a coating pressure-sensitive adhesive solution.
　続いて、この粘着剤溶液を、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムからなる基材２上に塗布した。そして、基材２上に塗布した粘着剤溶液を、乾燥炉の前半部において、４０～９０℃の温度にて段階的に初期乾燥し、さらに、乾燥炉の後半部に設けられた熱処理の最高温度が１６０℃となるゾーンで３分間乾燥させて粘着剤層３を加熱・硬化させ、乾燥後の厚さが２０μｍの粘着剤層３を形成した。次いで、フロロアルキル変性シリコーンで離型処理された剥離ライナーを粘着剤層３に貼合した。これにより、乾燥後の総厚が５８μｍの粘着テープ１を得た。 Subsequently, this pressure-sensitive adhesive solution was applied onto a base material 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Then, the pressure-sensitive adhesive solution applied on the base material 2 is initially dried stepwise at a temperature of 40 to 90 ° C. in the first half of the drying furnace, and further, the highest heat treatment provided in the second half of the drying furnace. The pressure-sensitive adhesive layer 3 was heated and cured by drying in a zone where the temperature was 160 ° C. for 3 minutes to form a pressure-sensitive adhesive layer 3 having a thickness of 20 μm after drying. Next, a release liner separated from the fluoroalkyl-modified silicone was attached to the pressure-sensitive adhesive layer 3. As a result, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.
　実施例１～１０、および比較例１～６で作製した粘着テープ１における層構成および粘着剤層３の組成を、表１～表３に示す。 Tables 1 to 3 show the layer structure and the composition of the pressure-sensitive adhesive layer 3 in the pressure-sensitive adhesive tapes 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
２．評価方法
　続いて、粘着テープ１の評価方法について説明する。
（１）粘着力試験（ＵＶ照射前）
　実施例１～１０および比較例１～６で作製した粘着テープ１について、粘着テープ・粘着シート試験方法（ＪＩＳ　Ｚ　０２３７（２００９））に記載された方法に準拠して、対ＢＡ－ＳＵＳ粘着力試験（引き剥がし粘着力試験）を行った。
　具体的には、剥離ライナーを剥がした粘着テープ１をブライトアニール（ＢＡ）処理した表面粗さ（Ｒａ）が５０±２５ｎｍのステンレス板（ＳＵＳ３０４）に貼り付け、質量２０００ｇのローラを５ｍｍ／ｓの速度で１往復させて、圧着した。続いて、２０～４０分放置した後、引張試験機を用いて、ステンレス板に対して１８０°方向へ５ｍｍ／ｓの速度で引き剥がし、研磨ＳＵＳ板に対する粘着力を測定した。
　なお、粘着力試験は、紫外線（ＵＶ）を照射する前の粘着テープ１に対して行った。また、粘着力試験の結果としては、粘着テープ１を半導体材料のダイシングに用いる場合の固定力を考慮すると、２．４Ｎ／１０ｍｍ以上であることが好ましく、ダイシングにより個片化された半導体チップ等のピックアップ性の観点から、５．５Ｎ／１０ｍｍ以下であることが好ましい。より好ましくは、２．８Ｎ／１０ｍｍ以上、５．５Ｎ／１０ｍｍ以下である。 2. Evaluation Method Subsequently, the evaluation method of the adhesive tape 1 will be described.
(1) Adhesive strength test (before UV irradiation)
Adhesive Tapes 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6 have adhesive strength against BA-SUS in accordance with the method described in the adhesive tape / adhesive sheet test method (JIS Z 0237 (2009)). A test (peeling adhesive strength test) was performed.
Specifically, the adhesive tape 1 from which the release liner has been peeled off is attached to a stainless steel plate (SUS304) having a surface roughness (Ra) of 50 ± 25 nm treated with bright annealing (BA), and a roller having a mass of 2000 g is attached to a roller having a mass of 5 mm / s. It was reciprocated once at a speed and crimped. Then, after leaving it to stand for 20 to 40 minutes, it was peeled off from the stainless steel plate at a speed of 5 mm / s in the 180 ° direction using a tensile tester, and the adhesive strength to the polished SUS plate was measured.
The adhesive strength test was performed on the adhesive tape 1 before it was irradiated with ultraviolet rays (UV). Further, as a result of the adhesive strength test, considering the fixing force when the adhesive tape 1 is used for dicing a semiconductor material, it is preferably 2.4 N / 10 mm or more, and a semiconductor chip or the like individualized by dicing or the like. From the viewpoint of pick-up property, it is preferably 5.5 N / 10 mm or less. More preferably, it is 2.8 N / 10 mm or more and 5.5 N / 10 mm or less.
（２）ボールタック試験
（２－１）初期（ＵＶ照射前）ボールタックの測定
　実施例１～１０および比較例１～６で作製したＵＶを照射する前の粘着テープ１について、粘着テープ・粘着シート試験方法（ＪＩＳ　Ｚ　０２３７（２００９））に記載された方法に準拠して、ボールタック試験を行った。 (2) Ball tack test (2-1) Initial (before UV irradiation) Ball tack measurement Adhesive tape / adhesive tape 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 before UV irradiation. The ball tack test was performed according to the method described in the sheet test method (JIS Z 0237 (2009)).
（２－２）ＵＶ照射後ボールタックの測定
　実施例１～１０および比較例１～６で作製したそれぞれの粘着テープ１の基材側からＵＶを照射し、温度２３℃、湿度５０±５％ＲＨの条件下で２０～４０分放置した後、それぞれの粘着テープ１の剥離ライナーを剥がし、粘着テープ・粘着シート試験方法（ＪＩＳ　Ｚ　０２３７（２００９））に記載された方法に準拠して、初期（ＵＶ照射前）ボールタックと同様にして、ボールタック試験を行った。
　ＵＶの照射は、高圧水銀ランプを用い、波長３６５ｎｍのＵＶが積算光量で１２００ｍＪ／ｃｍ2になるよう調整し照射した。なお、積算光量を３０００ｍＪ／ｃｍ2とした場合のボールタックについても同様に測定したが、積算光量を１２００ｍＪ／ｃｍ2とした場合との差が見られなかったため、ここでは、積算光量を１２００ｍＪ／ｃｍ2として評価を行った。 (2-2) Measurement of ball tack after UV irradiation UV is irradiated from the base material side of each of the adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6, and the temperature is 23 ° C. and the humidity is 50 ± 5%. After leaving it for 20 to 40 minutes under the condition of RH, the release liner of each adhesive tape 1 is peeled off, and the initial stage is based on the method described in the adhesive tape / adhesive sheet test method (JIS Z 0237 (2009)). A ball tack test was performed in the same manner as the ball tack (before UV irradiation).
The UV irradiation was performed by using a high-pressure mercury lamp and adjusting the UV having a wavelength of 365 nm so that the integrated light intensity was 1200 mJ / cm 2. Although was similarly measured for the ball tack when the cumulative amount of light with 3000 mJ / cm 2, the difference between the case where the cumulative amount of light with 1200 mJ / cm 2 was observed, here, the integrated light quantity of 1200 mJ / It was evaluated as cm 2.
　ボールタック試験の結果としては、ダイシングにより個片化された半導体チップ等のピックアップ性を考慮すると、初期（ＵＶ照射前）ボールタック（ボールＮｏ．）と比べてＵＶ照射後ボールタック（ボールＮｏ．）が低いことが好ましい。すなわち、ＵＶ照射前のボールナンバーの値をＢＮ０、ＵＶ照射後のボールナンバーの値をＢＮ１とした場合に、ＢＮ０＞ＢＮ１の関係であることが好ましい。この関係は、ＵＶ照射により粘着剤層３の２段階目の架橋反応が促進され、凝集力がＵＶ照射前よりも増大したことを意味する。 As a result of the ball tack test, considering the pick-up property of the semiconductor chip, etc., which was separated by dicing, the ball tack after UV irradiation (ball No.) was compared with the initial (before UV irradiation) ball tack (ball No.). ) Is preferably low. That is, when the value of the ball number before UV irradiation is BN0 and the value of the ball number after UV irradiation is BN1, the relationship of BN0> BN1 is preferable. This relationship means that the UV irradiation promoted the second-stage cross-linking reaction of the pressure-sensitive adhesive layer 3, and the cohesive force was increased as compared with that before the UV irradiation.
（３）保持力試験
（３－１）初期（ＵＶ照射前）保持力の測定
　実施例１～１０および比較例１～６で作製したＵＶを照射する前の粘着テープ１について、粘着テープ・粘着シート試験方法（ＪＩＳ　Ｚ　０２３７（２００９））に記載された方法に準拠して、保持力試験を行った。
　具体的には、それぞれの粘着テープ１の剥離ライナーを剥がし、粘着剤層３を、耐水研磨紙で研磨したステンレス板（ＳＵＳ３０４）に貼り付け、所定の重りを取り付けた状態で温度４０℃、湿度３３％ＲＨの条件下で保持し、粘着テープ１がステンレス板から剥離して落下するまでの経過時間（落下時間（分））を測定した。さらに、粘着テープ１がステンレス板から剥離した際の破壊モード（粘着剤層３とステンレス板との間の破壊モードが界面剥離であるか凝集破壊であるか）を観察した。なお、保持力試験における落下時間の測定は、２８８０分まで行った。また、後述する表４～表６に示す保持力試験の結果として、落下時間（分）および粘着テープ１の破壊モードを示している。 (3) Holding force test (3-1) Measurement of initial (before UV irradiation) Adhesive tape 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 before UV irradiation is adhered to the adhesive tape. The holding force test was performed according to the method described in the sheet test method (JIS Z 0237 (2009)).
Specifically, the release liner of each adhesive tape 1 is peeled off, the adhesive layer 3 is attached to a stainless plate (SUS304) polished with water-resistant abrasive paper, and a temperature of 40 ° C. and humidity are attached with a predetermined weight attached. The adhesive tape 1 was held under the condition of 33% RH, and the elapsed time (falling time (minutes)) until the adhesive tape 1 was peeled off from the stainless steel plate and dropped was measured. Further, the fracture mode when the adhesive tape 1 was peeled off from the stainless steel plate (whether the fracture mode between the adhesive layer 3 and the stainless steel plate was interfacial peeling or cohesive fracture) was observed. The drop time in the holding force test was measured up to 2880 minutes. Further, as a result of the holding force test shown in Tables 4 to 6 described later, the drop time (minutes) and the breaking mode of the adhesive tape 1 are shown.
（３－２）ＵＶ照射後保持力の測定
　上述したＵＶ照射後のボールタックの測定に記載した条件と同様にして、粘着テープ１にＵＶを照射し、放置した後、初期保持力と同様にして保持力試験を行った。 (3-2) Measurement of Retaining Power after UV Irradiation The adhesive tape 1 is irradiated with UV in the same manner as described in the above-mentioned measurement of ball tack after UV irradiation, left to stand, and then the same as the initial holding power. The holding power test was conducted.
（３－３）保持力と破壊モードとの関係について
　ここで、粘着テープ１の保持力と破壊モードとの関係について説明する。図３は、粘着剤層３におけるシリコーン系樹脂の架橋密度と、粘着テープ１の保持力試験の結果（落下時間）との関係を示した模式図である。
　図３に示すように、粘着テープ１では、粘着剤層３におけるシリコーン系樹脂の架橋密度が高くなるに従い、保持力試験による粘着テープ１のステンレス板に対する破壊モードが、［粘着剤層３の凝集破壊（落下）］→［保持（落下しない）］→［粘着剤層３とステンレス板との界面剥離（落下）］へと変化する。 (3-3) Relationship between Holding Force and Breaking Mode Here, the relationship between the holding power of the adhesive tape 1 and the breaking mode will be described. FIG. 3 is a schematic view showing the relationship between the crosslink density of the silicone-based resin in the pressure-sensitive adhesive layer 3 and the result (falling time) of the holding force test of the pressure-sensitive adhesive tape 1.
As shown in FIG. 3, in the adhesive tape 1, as the cross-linking density of the silicone-based resin in the adhesive layer 3 increases, the breaking mode of the adhesive tape 1 with respect to the stainless steel plate by the holding force test is changed to [Aggregation of the adhesive layer 3]. It changes in the order of [break (fall)] → [hold (do not fall)] → [intersection peeling (fall) between the adhesive layer 3 and the stainless steel plate].
　また、図３に示すように、粘着テープ１の破壊モードが凝集破壊である領域では、粘着テープ１の保持力（落下時間）は、粘着剤層３におけるシリコーン系樹脂の架橋密度が高くなるに従い上昇する。
　一方、図３に示すように、粘着テープ１の破壊モードが界面剥離である領域では、粘着テープ１の保持力（落下時間）は、粘着剤層３におけるシリコーン系樹脂の架橋密度が高くなるに従い低下する。これは、シリコーン系樹脂の架橋密度が高くなるに従って粘着剤層３の凝集力が上昇し、粘着テープ１の粘着力が低下して、結果として粘着テープがステンレス板から剥離して落下しやすくなるためであると推測される。 Further, as shown in FIG. 3, in the region where the fracture mode of the adhesive tape 1 is cohesive fracture, the holding force (falling time) of the adhesive tape 1 increases as the cross-linking density of the silicone-based resin in the adhesive layer 3 increases. To rise.
On the other hand, as shown in FIG. 3, in the region where the fracture mode of the adhesive tape 1 is interfacial peeling, the holding force (falling time) of the adhesive tape 1 increases as the cross-linking density of the silicone-based resin in the adhesive layer 3 increases. descend. This is because the cohesive force of the adhesive layer 3 increases as the cross-linking density of the silicone-based resin increases, the adhesive force of the adhesive tape 1 decreases, and as a result, the adhesive tape easily peels off from the stainless steel plate and falls off. It is presumed that this is the reason.
　保持力試験の結果としては、少なくともＵＶ照射後の破壊モードが保持または界面剥離であることが好ましく、少なくともＵＶ照射後の破壊モードが界面剥離であることがより好ましく、初期（ＵＶ照射前）およびＵＶ照射後の破壊モードがともに界面剥離であることがさらに好ましい。また、初期（ＵＶ照射前）とＵＶ照射後の破壊モードがともに界面剥離である場合には、落下時間は、初期（ＵＶ照射前）においては、粘着テープ１を半導体材料のダイシングに用いる場合の固定力の観点から、できるだけ長い、あるいは落下しないことが好ましく、ＵＶ照射後においては、ダイシングにより個片化された半導体チップ等のピックアップ性の観点から、初期（ＵＶ照射前）と比べて短いことが好ましい。
　この場合、粘着テープ１を半導体素子基板等のダイシングに使用した後、得られた半導体チップ等を粘着テープ１から剥離する際に、粘着テープ１にＵＶ照射することにより半導体チップ等に糊残りが生じにくくなる。 As a result of the holding power test, at least the destruction mode after UV irradiation is preferably retention or interfacial peeling, and at least the destruction mode after UV irradiation is more preferably interfacial peeling, and the initial (before UV irradiation) and It is more preferable that both destruction modes after UV irradiation are interfacial peeling. When both the initial (before UV irradiation) and post-UV irradiation destruction modes are interfacial peeling, the drop time is the initial (before UV irradiation) when the adhesive tape 1 is used for dicing the semiconductor material. From the viewpoint of fixing force, it is preferable that it is as long as possible or does not fall, and after UV irradiation, it is shorter than the initial stage (before UV irradiation) from the viewpoint of picking up semiconductor chips and the like that have been separated by dicing. Is preferable.
In this case, after the adhesive tape 1 is used for dicing the semiconductor element substrate or the like, when the obtained semiconductor chip or the like is peeled off from the adhesive tape 1, the adhesive tape 1 is irradiated with UV to leave adhesive residue on the semiconductor chip or the like. It is less likely to occur.
（４）対シリコーン樹脂糊残り試験
　実施例１～１０および比較例１～６で作製した粘着テープ１について、シリコーン樹脂に対する糊残り試験を行った。
　まず、ＬＥＤデバイス用シリコーン樹脂であるメチル基を含有するシリコーン樹脂（信越化学工業株式会社製ＫＥＲ－２５００Ｎ（商品名））のＡ剤とＢ剤とを混合比１：１で混合して混合液を作製した。この混合液を、ステンレス板に塗布し、１００℃×１時間、さらに１５０℃×２時間の条件で加熱し硬化させて、シリコーン試験片Ａを作製した。
　同様に、ＬＥＤデバイス用シリコーン樹脂であるフェニル基を含有するシリコーン樹脂（信越化学工業株式会社製のＫＥＲ－６１１０（商品名））のＡ剤とＢ剤とを混合比３：７で混合して混合液を作製した。この混合液を、ステンレス板に塗布し、１００℃×２時間、さらに１５０℃×５時間の条件で加熱し硬化させて、シリコーン試験片Ｂを作製した。 (4) Anti-Silicone Resin Adhesive Residual Test The adhesive tape 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6 was subjected to an adhesive residue test on a silicone resin.
First, agent A and agent B of a silicone resin containing a methyl group (KER-2500N (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone resin for LED devices, are mixed at a mixing ratio of 1: 1 to prepare a mixed solution. Was produced. This mixed solution was applied to a stainless steel plate and heated and cured under the conditions of 100 ° C. × 1 hour and further 150 ° C. × 2 hours to prepare a silicone test piece A.
Similarly, the A agent and the B agent of a silicone resin containing a phenyl group (KER-6110 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone resin for LED devices, are mixed at a mixing ratio of 3: 7. A mixed solution was prepared. This mixed solution was applied to a stainless steel plate and heated and cured under the conditions of 100 ° C. × 2 hours and further 150 ° C. × 5 hours to prepare a silicone test piece B.
　続いて、粘着テープ１の剥離ライナーを剥がし、粘着剤層３を、シリコーン試験片Ａ、Ｂにそれぞれ貼り付け、質量２０００ｇのローラを５ｍｍ／ｓの速度で１往復させて、圧着した。続いて、ＵＶ照射後のボールタックの測定に記載した条件と同様にして、粘着テープ１の基材２側からＵＶを照射した後、温度４０℃、湿度９０％ＲＨの環境下に１２０時間放置した。その後、室温にし、粘着テープ１を、シリコーン試験片Ａ、Ｂに対して９０°方向へ８００ｍｍ／ｓ～１２００ｍｍ／ｓの速度で引き剥がし、シリコーン試験片Ａ、Ｂに対する糊残りを目視で確認した。 Subsequently, the release liner of the adhesive tape 1 was peeled off, the adhesive layer 3 was attached to the silicone test pieces A and B, respectively, and a roller having a mass of 2000 g was reciprocated once at a speed of 5 mm / s and crimped. Subsequently, UV is irradiated from the base material 2 side of the adhesive tape 1 in the same manner as described in the measurement of ball tack after UV irradiation, and then left in an environment of a temperature of 40 ° C. and a humidity of 90% RH for 120 hours. did. Then, at room temperature, the adhesive tape 1 was peeled off at a speed of 800 mm / s to 1200 mm / s in the 90 ° direction with respect to the silicone test pieces A and B, and the adhesive residue on the silicone test pieces A and B was visually confirmed. ..
（５）対エポキシ樹脂糊残り試験
　実施例１～１０および比較例１～６で作製した粘着テープ１について、エポキシ樹脂に対する糊残り試験を行った。
　ガラスクロス基材にエポキシ樹脂を含侵させたエポキシ樹脂板（日光化成株式会社製ＮＬ－ＥＧ－２３（商品名））からなるエポキシ試験片に対して、剥離ライナーを剥がした粘着テープ１の粘着剤層３を貼り付け、質量２０００ｇのローラを５ｍｍ／ｓの速度で１往復させて、圧着した。続いて、ＵＶ照射後のボールタックの測定に記載した条件と同様にして、粘着テープ１の基材２側からＵＶを照射した後、温度４０℃、湿度９０％ＲＨの環境下に１２０時間放置した。その後、室温にし、粘着テープ１を、エポキシ試験片に対して９０°方向へ８００ｍｍ／ｓ～１２００ｍｍ／ｓの速度で引き剥がし、エポキシ試験片に対する糊残りを目視で確認した。 (5) Adhesive Residual Test Against Epoxy Resin The adhesive tape 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6 was subjected to an adhesive residue test on an epoxy resin.
Adhesive tape 1 with the release liner peeled off from an epoxy test piece made of an epoxy resin plate (NL-EG-23 (trade name) manufactured by Nikko Kasei Co., Ltd.) in which an epoxy resin is impregnated in a glass cloth base material. The agent layer 3 was attached, and a roller having a mass of 2000 g was reciprocated once at a speed of 5 mm / s and pressure-bonded. Subsequently, UV is irradiated from the base material 2 side of the adhesive tape 1 in the same manner as described in the measurement of ball tack after UV irradiation, and then left in an environment of a temperature of 40 ° C. and a humidity of 90% RH for 120 hours. did. Then, at room temperature, the adhesive tape 1 was peeled off from the epoxy test piece in the 90 ° direction at a speed of 800 mm / s to 1200 mm / s, and the adhesive residue on the epoxy test piece was visually confirmed.
　対シリコーン樹脂糊残り試験、および対エポキシ樹脂糊残り試験は、以下の判断基準で評価を行った。なお、ＡまたはＢの評価を合格とした。
　Ａ：試験片の単位面積当たり１００％の範囲で糊残りなし
　Ｂ：試験片の単位面積当たり２％未満の範囲で糊残りが見られる
　Ｃ：試験片の単位面積当たり２％以上５％未満の範囲で糊残りが見られる
　Ｄ：試験片の単位面積当たり５％以上の範囲で糊残りが見られる、または、試験片のエッジ部分に糊残りが見られる The anti-silicone resin adhesive residue test and the anti-epoxy resin adhesive residue test were evaluated according to the following criteria. The evaluation of A or B was accepted.
A: No adhesive residue in the range of 100% per unit area of the test piece B: Adhesive residue is seen in the range of less than 2% per unit area of the test piece C: 2% or more and less than 5% per unit area of the test piece Adhesive residue is seen in the range D: Adhesive residue is seen in the range of 5% or more per unit area of the test piece, or glue residue is seen at the edge part of the test piece.
（６）ダイシング試験
　実施例１～１０および比較例１～６で作製した粘着テープ１について、ダイシング試験を行った。
　具体的には、まず、モールド用エポキシ樹脂（日立化成株式会社製ＣＥＬ－４００ＺＨＦ４０－Ｗ７５Ｇ（商品名））を金型に入れ、封止圧力５０ｋｇｆ/ｃｍ2（４９１Ｎ／ｃｍ2）、封止材の厚さ０．３ｍｍ、加熱温度１５０℃×３００秒の条件で加熱硬化させ、円板状（直径２００ｍｍ（８インチ））のダイシング試験片を作製した。
　続いて、剥離ライナーを剥がした粘着テープ１の粘着剤層３をダイシング用リングに貼り付け、リングからはみ出した部分を切り取った後、さらにフッ素系剥離フィルム（ニッパ株式会社製ＳＳ１Ａ（商品名）、厚さ７５μｍ）に貼り合わせた。続いて、質量２０００ｇのローラを往復させて、粘着テープ１とリング部分とを圧着した。続いて、フッ素系剥離フィルムを剥がし、リング中央部分の粘着剤層３にダイシング試験片を貼り合わせ、圧着した。 (6) Dicing test A dicing test was carried out on the adhesive tape 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6.
Specifically, first, an epoxy resin for molding (CEL-400ZHF40-W75G (trade name) manufactured by Hitachi Kasei Co., Ltd.) is placed in a mold, a sealing pressure of 50 kgf / cm 2 (491 N / cm 2 ), and a sealing material. A disk-shaped (diameter 200 mm (8 inches)) dicing test piece was prepared by heating and curing under the conditions of a thickness of 0.3 mm and a heating temperature of 150 ° C. × 300 seconds.
Subsequently, the adhesive layer 3 of the adhesive tape 1 from which the release liner was peeled off was attached to the dicing ring, and after cutting off the portion protruding from the ring, a fluorine-based release film (SS1A (trade name) manufactured by Nippa Corporation), It was bonded to a thickness of 75 μm). Subsequently, a roller having a mass of 2000 g was reciprocated to crimp the adhesive tape 1 and the ring portion. Subsequently, the fluorine-based release film was peeled off, and the dicing test piece was attached to the pressure-sensitive adhesive layer 3 at the center of the ring and pressure-bonded.
　さらに、東京精密株式会社製ダイシング装置（Ａ－ＷＤ－１００Ａ（商品名））を用いて、株式会社ディスコ製のダイシングブレードにて、ダイシング試験片を粘着テープ１とともに１０ｍｍ×１０ｍｍのチップに切断した。この際、飛散したチップの個数を計測し、ダイシング試験における固定力の評価を行った。
　続いて、１０ｍｍ×１０ｍｍに個片化したチップに貼り付けられた粘着テープ１に対して、ＵＶ照射後ボールタックの測定に記載した条件と同様にして、ＵＶを照射した。その後、粘着テープ１から個片化したチップをピックアップし、チップへの糊残りの有無を目視で確認して、ダイシング試験における糊残りの評価を行った。また、チップをピックアップした際に、ピックアップに失敗したチップの個数を計測して、ダイシング試験におけるピックアップ性の評価を行った。 Further, using a dicing device manufactured by Tokyo Seimitsu Co., Ltd. (A-WD-100A (trade name)), a dicing test piece was cut into a 10 mm × 10 mm chip together with the adhesive tape 1 with a dicing blade manufactured by Disco Corporation. .. At this time, the number of scattered chips was measured and the fixing force in the dicing test was evaluated.
Subsequently, the adhesive tape 1 attached to the chip pieced into pieces of 10 mm × 10 mm was irradiated with UV in the same conditions as described in the measurement of ball tack after UV irradiation. Then, the individualized chips were picked up from the adhesive tape 1, and the presence or absence of adhesive residue on the chip was visually confirmed to evaluate the adhesive residue in the dicing test. In addition, when the chips were picked up, the number of chips that failed to be picked up was measured to evaluate the pick-up property in the dicing test.
　ダイシング試験における固定力は、以下の判断基準で評価を行った。なお、ＡまたはＢの評価を合格とした。
　Ａ：飛散したチップの数が１００個中０個で、チップの欠けが認められない
　Ｂ：飛散したチップの数が１００個中１個で、チップの欠けが認められない
　Ｃ：飛散したチップの数が１００個中２個で、チップの欠けが認められない
　Ｄ：飛散したチップの数が１００個中３個以上、あるいはチップの欠けが認められる The fixing force in the dicing test was evaluated according to the following criteria. The evaluation of A or B was accepted.
A: The number of scattered chips is 0 out of 100 and no chip chipping is observed. B: The number of scattered chips is 1 out of 100 and no chip chipping is observed. C: The number of scattered chips is not recognized. The number is 2 out of 100, and no chip chipping is observed. D: The number of scattered chips is 3 or more out of 100, or chip chipping is observed.
　ダイシング試験における糊残りは、以下の判断基準で評価を行った。なお、Ａの評価を合格とした。
　Ａ：チップに糊残りが見られない
　Ｄ：チップに糊残りが見られる、またはチップの側面に粘着剤の糸曳が見られる The adhesive residue in the dicing test was evaluated according to the following criteria. The evaluation of A was passed.
A: No adhesive residue is seen on the tip D: Adhesive residue is seen on the tip, or adhesive threading is seen on the side of the tip.
　ダイシング試験におけるピックアップ性は、以下の判断基準で評価を行った。なお、ＡまたはＢの評価を合格とした。
　Ａ：ピックアップに失敗したチップの個数が１００個中０個
　Ｂ：ピックアップに失敗したチップの個数が１００個中１個
　Ｃ：ピックアップに失敗したチップの個数が１００個中２個
　Ｄ：ピックアップに失敗したチップの個数が１００個中３個以上 The pick-up property in the dicing test was evaluated according to the following criteria. The evaluation of A or B was accepted.
A: 0 out of 100 chips failed to pick up B: 1 out of 100 chips failed to pick up C: 2 out of 100 chips failed to pick up D: failed to pick up 3 or more out of 100 chips
３．試験結果
　実施例１～１０、および比較例１～６の粘着テープ１に対する評価結果について、表４～６に示す。 3. 3. Test Results Tables 4 to 6 show the evaluation results for the adhesive tape 1 of Examples 1 to 10 and Comparative Examples 1 to 6.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表４、５に示すように、粘着剤層が、本発明の要件を満足する実施例１～１０の粘着テープ１では、粘着力試験、ボールタック試験、保持力試験、対シリコーン樹脂糊残り試験、対エポキシ樹脂糊残り試験、およびダイシング試験（固定力、糊残りおよびピックアップ性）のいずれにおいても好ましい結果が得られることが確認された。 As shown in Tables 4 and 5, in the adhesive tapes 1 of Examples 1 to 10 in which the adhesive layer satisfies the requirements of the present invention, the adhesive strength test, the ball tack test, the holding force test, and the silicone resin adhesive residue test , It was confirmed that favorable results were obtained in all of the epoxy resin adhesive residue test and the dicing test (fixing force, adhesive residue and pick-up property).
　これにより、実施例１～１０の粘着テープ１は、半導体材料のダイシング用粘着テープ、より具体的には、半導体素子基板の封止樹脂側から貼り付けてダイシングに使用するダイシング用粘着テープとして有用であることが確認された。 Thereby, the adhesive tape 1 of Examples 1 to 10 is useful as an adhesive tape for dicing of a semiconductor material, more specifically, an adhesive tape for dicing which is attached from the sealing resin side of the semiconductor element substrate and used for dicing. It was confirmed that.
　中でも、シリコーン系樹脂全体におけるケイ素原子結合アルケニル基の含有量が、２．９×１０-6ｍｏｌ／ｇ以上４．１×１０-6ｍｏｌ／ｇ以下の範囲である実施例５、７および１０の粘着テープ１は、他の実施例の粘着テープ１と比べて、全ての試験項目において評価結果が良好であった。なお、この実施例５、７および１０のシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））は、４１．５／５８．５～５０．４／４９．６の範囲であった。 Among them, Examples 5, 7 and 10 in which the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 2.9 × 10 -6 mol / g or more and 4.1 × 10 -6 mol / g or less. The adhesive tape 1 of No. 1 had better evaluation results in all the test items than the adhesive tape 1 of the other examples. The mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) of Examples 5, 7 and 10 is 41.5 / 58.5 to 50.4 / 49. It was in the range of 0.6.
　これに対し、表６に示すように、粘着剤層３が本発明の要件を満たさない比較例１～６の粘着テープ１は、対シリコーン樹脂糊残り試験、対エポキシ樹脂糊残り試験、およびダイシング試験（固定力、糊残りおよびピックアップ性）において、いずれかの試験結果が実施例１～１０より劣る結果であることが確認された。 On the other hand, as shown in Table 6, the adhesive tapes 1 of Comparative Examples 1 to 6 in which the pressure-sensitive adhesive layer 3 does not satisfy the requirements of the present invention are subjected to a silicone resin adhesive residue test, an epoxy resin adhesive residue test, and dicing. In the tests (fixing force, adhesive residue and pick-up property), it was confirmed that any of the test results was inferior to that of Examples 1 to 10.
　具体的には、粘着剤層３が架橋剤および熱重合開始剤を含まない比較例１の粘着テープ１では、加熱あるいはＵＶ照射を施してもシリコーン系樹脂の架橋反応が起こらないため、ＵＶ照射前後で、ボールタック試験および保持力試験の結果には変化は見られず、凝集力が不足していた。そのため、実用性確認のための対シリコーン樹脂糊残り試験および対エポキシ樹脂糊残り試験および対エポキシ樹脂糊残り試験において、糊残りが多く見られた。また、ダイシング試験においては、上述のようにＵＶ照射後の凝集力の増大が認められなかったので、ダイシンング試験片のチップのピックアップ性が劣り、チップに糊残りが見られた。 Specifically, in the adhesive tape 1 of Comparative Example 1 in which the pressure-sensitive adhesive layer 3 does not contain a cross-linking agent and a thermal polymerization initiator, the cross-linking reaction of the silicone-based resin does not occur even if it is heated or UV-irradiated. Before and after, there was no change in the results of the ball tack test and the holding force test, and the cohesive force was insufficient. Therefore, a large amount of adhesive residue was observed in the silicone resin adhesive residue test, the epoxy resin adhesive residue test, and the epoxy resin adhesive residue test for confirming practicality. Further, in the dicing test, since the increase in the cohesive force after UV irradiation was not observed as described above, the pick-up property of the chip of the dicing test piece was inferior, and adhesive residue was observed on the chip.
　また、粘着剤層３が光感応白金（Ｐｔ）触媒を含まず、通常の白金（Ｐｔ）触媒を含む比較例２の粘着テープ１では、ＵＶ照射前の初期においては、凝集力は増大するが、ＵＶ照射を施しても凝集力が増大することはなく、ＵＶ照射前後で、ボールタック試験および保持力試験の結果には変化は見られなかった。そのため、対シリコーン樹脂糊残り試験および対エポキシ樹脂糊残り試験において、糊残りが多く見られた。また、ダイシング試験においても、ダイシンング試験片のチップのピックアップ性がやや劣り、チップに糊残りがやや多く見られた。 Further, in the adhesive tape 1 of Comparative Example 2 in which the pressure-sensitive adhesive layer 3 does not contain a photosensitive platinum (Pt) catalyst and contains a normal platinum (Pt) catalyst, the cohesive force increases in the initial stage before UV irradiation. The cohesive force did not increase even after UV irradiation, and no change was observed in the results of the ball tack test and the holding force test before and after UV irradiation. Therefore, a large amount of adhesive residue was observed in the silicone resin adhesive residue test and the epoxy resin adhesive residue test. Also, in the dicing test, the pick-up property of the chip of the dicing test piece was slightly inferior, and a little adhesive residue was observed on the chip.
　さらに、粘着剤層３中のシリコーン系樹脂におけるケイ素原子結合アルケニル基の含有量が、本発明の要件の下限値未満である比較例３の粘着テープ１では、ＵＶ照射前後で、ボールタック試験および保持力試験の結果には変化は見られず、ＵＶ照射による粘着剤層３の凝集力の増大効果が不十分であった。そのため、対シリコーン樹脂糊残り試験および対エポキシ樹脂糊残り試験において、糊残りが多く見られた。また、ダイシング試験においても、ダイシンング試験片のチップのピックアップ性が劣り、チップに糊残りが見られた。 Further, in the pressure-sensitive adhesive tape 1 of Comparative Example 3 in which the content of the silicon atom-bonded alkenyl group in the silicone-based resin in the pressure-sensitive adhesive layer 3 is less than the lower limit of the requirements of the present invention, a ball tack test and a ball tack test are performed before and after UV irradiation. No change was observed in the results of the holding power test, and the effect of increasing the cohesive power of the pressure-sensitive adhesive layer 3 by UV irradiation was insufficient. Therefore, a large amount of adhesive residue was observed in the silicone resin adhesive residue test and the epoxy resin adhesive residue test. Also, in the dicing test, the pick-up property of the chip of the dicing test piece was inferior, and adhesive residue was observed on the chip.
　さらにまた、粘着剤層３中のシリコーン系樹脂におけるケイ素原子結合アルケニル基の含有量が、本発明の要件の上限値を超える比較例４の粘着テープ１では、ダイシング試験において、ダイシング試験片の固定力が低く、ダイシング時にチップの飛散が多く見られた。これは、ＵＶ照射前の段階、すなわち、粘着剤層３を基材２上に形成するための加熱・乾燥工程で、既に粘着剤層３中のシリコーン系樹脂のシリコーンガム（Ｇ）の架橋反応が熱重合開始剤により進行し、硬化して硬くなり過ぎたためと推測される。なお、対シリコーン樹脂糊残り試験および対エポキシ樹脂糊残り試験において糊残りは見られなかった。また、ダイシング試験においても、飛散しなかったチップについては、糊残りは見られなかった。 Furthermore, in the adhesive tape 1 of Comparative Example 4 in which the content of the silicon atom-bonded alkenyl group in the silicone-based resin in the adhesive layer 3 exceeds the upper limit of the requirements of the present invention, the dicing test piece is fixed in the dicing test. The force was low, and many chips were scattered during dicing. This is a step before UV irradiation, that is, a heating / drying step for forming the pressure-sensitive adhesive layer 3 on the base material 2, and a cross-linking reaction of the silicone gum (G) of the silicone-based resin already in the pressure-sensitive adhesive layer 3. It is presumed that this was due to the progress of the thermal polymerization initiator, which was cured and became too hard. No adhesive residue was found in the silicone resin adhesive residue test and the epoxy resin adhesive residue test. Also, in the dicing test, no adhesive residue was found on the chips that did not scatter.
　さらにまた、シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が本発明の要件の下限値未満である比較例５の粘着テープ１では、粘着剤層３の架橋にほとんど寄与しないシリコーンレジン（Ｒ）が多いので、ＵＶ照射による粘着剤層３の凝集力の増大効果が不十分であった。そのため、対シリコーン樹脂糊残り試験および対エポキシ樹脂糊残り試験において、糊残りがやや多く見られた。また、ダイシング試験においても、ダイシンング試験片のチップのピックアップ性がやや劣り、チップに糊残りがやや多く見られた。 Furthermore, in the adhesive tape 1 of Comparative Example 5 in which the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) is less than the lower limit of the requirements of the present invention, the adhesive layer Since there are many silicone resins (R) that hardly contribute to the cross-linking of No. 3, the effect of increasing the cohesive force of the pressure-sensitive adhesive layer 3 by UV irradiation was insufficient. Therefore, in the anti-silicone resin adhesive residue test and the anti-epoxy resin adhesive residue test, a slightly large amount of adhesive residue was observed. Also, in the dicing test, the pick-up property of the chip of the dicing test piece was slightly inferior, and a little adhesive residue was observed on the chip.
　さらにまた、粘着剤層３中のシリコーン系樹脂におけるシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が、本発明の要件の上限値を超える比較例６の粘着テープ１では、ダイシング試験において、ダイシング試験片の固定力が低く、ダイシング時にチップの飛散が多く見られた。これは、ＵＶ照射前の段階、すなわち、粘着剤層３を基材２上に形成するための加熱・乾燥工程で、既に粘着剤層３中のシリコーン系樹脂のシリコーンガム（Ｇ）の架橋反応が熱重合開始剤により進行し、硬化して硬くなり過ぎたためと推測される。なお、対シリコーン樹脂糊残り試験および対エポキシ樹脂糊残り試験において糊残りは見られなかった。また、ダイシング試験においても、飛散しなかったチップについては、糊残りは見られなかった。 Furthermore, a comparative example in which the mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) in the silicone-based resin in the pressure-sensitive adhesive layer 3 exceeds the upper limit of the requirements of the present invention. In the adhesive tape 1 of No. 6, the fixing force of the dicing test piece was low in the dicing test, and many chips were scattered during dicing. This is a step before UV irradiation, that is, a heating / drying step for forming the pressure-sensitive adhesive layer 3 on the base material 2, and a cross-linking reaction of the silicone gum (G) of the silicone-based resin already in the pressure-sensitive adhesive layer 3. It is presumed that this was due to the progress of the thermal polymerization initiator, which was cured and became too hard. No adhesive residue was found in the silicone resin adhesive residue test and the epoxy resin adhesive residue test. Also, in the dicing test, no adhesive residue was found on the chips that did not scatter.
１…粘着テープ、２…基材、３…粘着剤層、１００…半導体素子基板、１０１…基板、１０２…半導体素子、１０３…封止樹脂、２００…半導体チップ 1 ... Adhesive tape, 2 ... Base material, 3 ... Adhesive layer, 100 ... Semiconductor element substrate, 101 ... Substrate, 102 ... Semiconductor element, 103 ... Encapsulating resin, 200 ... Semiconductor chip

Claims (9)

  1. 　基材と当該基材に積層される粘着剤層とを備え、被覆材で被覆された複数の半導体素子を有する半導体材料を、複数の半導体チップに分割する際に使用されるダイシング用粘着テープであって、
    　前記粘着剤層は、
    　シリコーンガム（Ｇ）とシリコーンレジン（Ｒ）とが混合されたシリコーン系樹脂、当該シリコーン系樹脂に対する架橋剤として１分子中に少なくとも２個以上のケイ素原子結合水素原子（ＳｉＨ基）を有するオルガノポリシロキサン、熱重合開始剤として過酸化物、および光感応白金（Ｐｔ）触媒を含む粘着剤組成物からなり、
    　前記シリコーン系樹脂全体におけるシリコーンガム（Ｇ）とシリコーンレジン（Ｒ）との混合比率（（Ｇ）／（Ｒ））が、質量比で４０．０／６０．０～５６．０／４４．０の範囲であり、
    　前記シリコーンガム（Ｇ）が、ケイ素原子結合アルケニル基を含有するオルガノポリシロキサンからなるシリコーンガム（Ｇalk）を含み、
    　前記シリコーン系樹脂全体における前記ケイ素原子結合アルケニル基の含有量が、７．０×１０-7ｍｏｌ／ｇ以上５．５×１０-6ｍｏｌ／ｇ以下の範囲であることを特徴とするダイシング用粘着テープ。     An adhesive tape for dicing used when a semiconductor material having a base material and an adhesive layer laminated on the base material and having a plurality of semiconductor elements coated with a coating material is divided into a plurality of semiconductor chips. There,
    The pressure-sensitive adhesive layer
    A silicone-based resin in which silicone gum (G) and silicone resin (R) are mixed, and an organopoly having at least two or more silicon atom-bonded hydrogen atoms (SiH groups) in one molecule as a cross-linking agent for the silicone-based resin. It consists of a pressure-sensitive adhesive composition containing a siloxane, a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst.
    The mixing ratio ((G) / (R)) of the silicone gum (G) and the silicone resin (R) in the entire silicone resin is 40.0 / 60.0 to 56.0 / 44.0 in terms of mass ratio. Is in the range of
    The silicone gum (G) contains a silicone gum (G alk ) made of an organopolysiloxane containing a silicon atom-bonded alkenyl group.
    For dicing, the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 7.0 × 10 -7 mol / g or more and 5.5 × 10 -6 mol / g or less. Adhesive tape.
  2. 　複数の前記半導体素子がシリコーン樹脂からなる前記被覆材により封止された前記半導体材料に対して、当該被覆材側から貼り付けられて使用されることを特徴とする請求項１に記載のダイシング用粘着テープ。 The dicing application according to claim 1, wherein the plurality of the semiconductor elements are attached to the semiconductor material sealed with the coating material made of a silicone resin from the coating material side. Adhesive tape.
  3. 　前記粘着剤層は、前記粘着剤組成物に含まれる前記シリコーン系樹脂全体における前記ケイ素原子結合アルケニル基の含有量（総量）に対する、当該粘着剤組成物に含まれる前記架橋剤の前記ケイ素原子結合水素原子（ＳｉＨ基）の含有量（総量）のモル比率（ＳｉＨ基／ケイ素原子結合アルケニル基）が、２．０以上１０．０以下の範囲であることを特徴とする請求項１または２に記載のダイシング用粘着テープ。 The pressure-sensitive adhesive layer has the silicon atom bond of the cross-linking agent contained in the pressure-sensitive adhesive composition with respect to the content (total amount) of the silicon atom-bonded alkenyl group in the entire silicone-based resin contained in the pressure-sensitive adhesive composition. According to claim 1 or 2, the molar ratio (SiH group / silicon atom-bonded alkenyl group) of the content (total amount) of the hydrogen atom (SiH group) is in the range of 2.0 or more and 10.0 or less. The described adhesive tape for dying.
  4. 　前記粘着剤層は、前記粘着剤組成物における前記過酸化物の含有量が、前記シリコーン系樹脂全体の固形分１００質量部に対し、固形分で０．１０質量部以上３．００質量部以下の範囲であることを特徴とする請求項１乃至３のいずれか１項に記載のダイシング用粘着テープ。 In the pressure-sensitive adhesive layer, the content of the peroxide in the pressure-sensitive adhesive composition is 0.10 parts by mass or more and 3.00 parts by mass or less in terms of solid content with respect to 100 parts by mass of solid content of the entire silicone-based resin. The adhesive tape for dicing according to any one of claims 1 to 3, wherein the adhesive tape is in the range of.
  5. 　前記粘着剤層は、前記過酸化物がジアシルパーオキサイド類であることを特徴とする請求項１乃至４のいずれか１項に記載のダイシング用粘着テープ。 The adhesive tape for dicing according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive layer is a diacyl peroxide.
  6. 　前記粘着剤層は、前記粘着剤組成物における前記光感応白金（Ｐｔ）触媒の含有量が、前記シリコーン系樹脂全体の固形分１００質量部に対し、固形分で０．１０質量部以上３．００質量部以下の範囲であることを特徴とする請求項１乃至５のいずれか１項に記載のダイシング用粘着テープ。 In the pressure-sensitive adhesive layer, the content of the photosensitive platinum (Pt) catalyst in the pressure-sensitive adhesive composition is 0.10 parts by mass or more in terms of solid content with respect to 100 parts by mass in solid content of the entire silicone-based resin. The adhesive tape for dicing according to any one of claims 1 to 5, which is in the range of 00 parts by mass or less.
  7. 　前記粘着剤層は、前記シリコーン系樹脂全体における前記ケイ素原子結合アルケニル基の含有量が、２．９×１０-6ｍｏｌ／ｇ以上４．１×１０-6ｍｏｌ／ｇ以下の範囲であることを特徴とする請求項１乃至６のいずれか１項に記載のダイシング用粘着テープ。 In the pressure-sensitive adhesive layer, the content of the silicon atom-bonded alkenyl group in the entire silicone-based resin is in the range of 2.9 × 10 -6 mol / g or more and 4.1 × 10 -6 mol / g or less. The adhesive tape for dicing according to any one of claims 1 to 6, wherein the adhesive tape is used for dicing.
  8. 　ＪＩＳ　Ｚ　０２３７（２００９）に準拠した粘着特性において下記条件（ａ）～（ｃ）の全てを満たすことを特徴とする請求項１乃至７のいずれか１項に記載のダイシング用粘着テープ。
    （ａ）ＢＡ－ＳＵＳ試験板に対する光照射前の粘着力は、２．８Ｎ／１０ｍｍ以上５．５Ｎ／１０ｍｍ以下の範囲であること。
    （ｂ）傾斜式ボールタック試験（傾斜角３０°、温度２３℃、相対湿度５０％ＲＨ）におけるボールナンバーの値は、光照射前のボールナンバーの値をＢＮ０、光照射後のボールナンバーの値をＢＮ１とした場合に、ＢＮ０＞ＢＮ１の関係であること。
    （ｃ）光照射後の保持力試験（温度４０℃、相対湿度３３％ＲＨ、放置時間２８８０分）において、落下時の破壊現象は、前記粘着剤層とＢＡ－ＳＵＳ試験板との界面剥離であること、もしくは、当該保持力試験において落下しないこと。     The adhesive tape for dicing according to any one of claims 1 to 7, wherein the adhesive characteristics conforming to JIS Z 0237 (2009) satisfy all of the following conditions (a) to (c).
    (A) The adhesive strength of the BA-SUS test plate before light irradiation shall be in the range of 2.8 N / 10 mm or more and 5.5 N / 10 mm or less.
    (B) The ball number values in the tilted ball tack test (tilt angle 30 °, temperature 23 ° C., relative humidity 50% RH) are the ball number value before light irradiation as BN0 and the ball number value after light irradiation. When is BN1, the relationship is BN0> BN1.
    (C) In the holding power test after light irradiation (temperature 40 ° C., relative humidity 33% RH, leaving time 2880 minutes), the fracture phenomenon at the time of dropping is the interface peeling between the adhesive layer and the BA-SUS test plate. There is, or it does not fall in the holding force test.
  9. 　請求項１乃至８のいずれか１項に記載のダイシング用粘着テープを、シリコーン樹脂からなる封止樹脂で封止された複数の前記半導体素子が基板上に形成された半導体素子基板に対して、当該封止樹脂側から貼り付ける貼付工程と、
    　前記ダイシング用粘着テープが貼り付けられた前記半導体素子基板を、複数の半導体チップに切断する切断工程と、
    　前記半導体素子基板の前記ダイシング用粘着テープに光を照射する照射工程と、
    　前記複数の半導体チップから、前記ダイシング用粘着テープを剥がす剥離工程と
    を含む半導体チップの製造方法。     The dicing adhesive tape according to any one of claims 1 to 8 is applied to a semiconductor device substrate in which a plurality of the semiconductor elements sealed with a sealing resin made of a silicone resin are formed on the substrate. The sticking process of sticking from the sealing resin side and
    A cutting step of cutting the semiconductor element substrate to which the adhesive tape for dicing is attached into a plurality of semiconductor chips, and
    An irradiation step of irradiating the dicing adhesive tape of the semiconductor element substrate with light,
    A method for manufacturing a semiconductor chip, which comprises a peeling step of peeling the adhesive tape for dicing from the plurality of semiconductor chips.
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