WO2022209152A1 - Ruban adhésif pour le traitement d'une pièce à usiner - Google Patents

Ruban adhésif pour le traitement d'une pièce à usiner Download PDF

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Publication number
WO2022209152A1
WO2022209152A1 PCT/JP2022/001414 JP2022001414W WO2022209152A1 WO 2022209152 A1 WO2022209152 A1 WO 2022209152A1 JP 2022001414 W JP2022001414 W JP 2022001414W WO 2022209152 A1 WO2022209152 A1 WO 2022209152A1
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Prior art keywords
meth
mass
parts
acrylic acid
acid ester
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Ceased
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PCT/JP2022/001414
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English (en)
Japanese (ja)
Inventor
邦生 齋藤
宗弘 守本
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Maxell Ltd
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Maxell Ltd
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Priority to KR1020237032325A priority Critical patent/KR102939115B1/ko
Priority to CN202280025102.1A priority patent/CN117157369A/zh
Publication of WO2022209152A1 publication Critical patent/WO2022209152A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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]
    • 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
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • H10P72/7402—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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/003—Presence of (meth)acrylic polymer in the primer coating

Definitions

  • the present invention relates to a work processing adhesive tape that can be suitably used when processing a work such as a semiconductor wafer or a glass substrate.
  • a semiconductor wafer having a circuit formed on its surface is ground from the back side to a predetermined thickness by a grinding wheel to thin the semiconductor wafer (hereinafter referred to as back grinding).
  • back grinding a grinding wheel to thin the semiconductor wafer
  • cutting a dicing process for singulating a semiconductor wafer into semiconductor chips
  • cutting a dicing process for singulating a glass substrate into glass chips
  • adhesive tapes used for grinding or cutting workpieces such as semiconductor wafers and glass plates
  • adhesive tapes used for grinding or cutting workpieces include, for example, back grind tapes having an active energy ray-curable adhesive layer on a base film, and Adhesive tape for work processing such as dicing tape can be used.
  • the backgrinding tape is used to stably hold and fix the semiconductor wafer and protect the circuit surface in the backgrinding process.
  • a specific usage method is as follows. First, a back grind tape is attached to the side of the semiconductor wafer on which the circuit is formed to fix the semiconductor wafer, and the back side of the semiconductor wafer is ground to a predetermined thickness by spraying water with a grinding wheel. After the grinding process is completed, the adhesive layer of the back grind tape is irradiated with active energy rays such as ultraviolet (UV) rays to reduce the adhesive strength, and the back grind tape is peeled off from the semiconductor wafer.
  • active energy rays such as ultraviolet (UV) rays
  • the dicing tape is used when the semiconductor wafer thinned by grinding in the back grinding process is cut into a predetermined size, for example, by a rotating dicing blade and singulated into individual semiconductor chips. It is used to fix the separated semiconductor wafer so that it does not shift, and to prevent the separated semiconductor chips from scattering.
  • a specific usage method is as follows. First, after attaching a dicing tape to the ring frame, a thin semiconductor wafer is attached and placed on the adhesive layer. Then, for the purpose of removing inevitably generated chips, etc., the cutting process is performed while supplying running water toward the dicing blade and the semiconductor wafer so as to separate the semiconductor wafer into individual pieces of a predetermined size.
  • the adhesive layer of the dicing tape is irradiated with active energy rays such as ultraviolet rays (UV) to reduce the adhesive force, and the individualized semiconductor chips are picked up from the adhesive layer by a pick-up device. .
  • active energy rays such as ultraviolet rays (UV)
  • the dicing tape is manually peeled off from the ring frame. The ring frame from which the dicing tape has been removed is washed and reused.
  • dicing unlike the case of semiconductor wafers, for example, in order to dice a fragile and fragile work such as a glass substrate or a hard work such as a sapphire glass/quartz substrate, dicing with less deformation during dicing than in the past is required. A tape is requested. That is, if the deformation of the dicing tape during dicing is large, the glass substrate cannot withstand the deformation and breaks, causing chipping (chipping of the edge or cut surface of the glass chip) or chip flying. Substrate quality problems may occur.
  • the chips when a hard sapphire glass substrate is diced, the chips may be misaligned, chipping may occur due to collision between the chips, pick-up errors of the chips may occur, and the dimensional accuracy of the chips may deteriorate.
  • a polyester film such as a polyethylene terephthalate film, which has a large tensile modulus and is relatively hard, as the base film (Patent Document 2).
  • a polyester film such as a polyethylene terephthalate film at least as the base film.
  • the conventional method using a relatively flexible and stretchable base film such as a polyolefin film is used. In some cases, the adhesiveness between the base film and the active energy ray-curable pressure-sensitive adhesive layer was insufficient compared to the back grind tape and dicing tape.
  • the active energy ray-curable pressure-sensitive adhesive layer is three-dimensionally polymerized and cured by irradiation with an active energy ray, causing volume shrinkage from the normal state before curing, and having a large elastic modulus.
  • a workpiece such as a semiconductor wafer or a glass chip can be easily separated from the adhesive layer.
  • the relatively flexible and stretchable polyolefin film can follow the volume shrinkage of the pressure-sensitive adhesive layer to some extent, the adhesion between the active energy ray-curable pressure-sensitive adhesive and the polyolefin film is maintained, but the surface A highly smooth and rigid polyester film is difficult to follow the volume shrinkage of the pressure-sensitive adhesive layer, and thus the adhesion between the active energy ray-curable pressure-sensitive adhesive layer and the polyester film may decrease.
  • the active energy ray-curable pressure-sensitive adhesive may be interfacially peeled from the polyester film, and the energy ray-curable pressure-sensitive adhesive may be transferred to the surface of the semiconductor wafer.
  • Patent Document 1 provides a pressure-sensitive adhesive sheet in which the energy-ray-curable pressure-sensitive adhesive layer is not transferred to a wafer or the like even when a polyester film is used as the base material of the energy-ray-curable pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive sheet is disclosed in which a polyester base film, an anchor coat layer containing a compound having an energy ray-polymerizable group, and an energy ray-curable pressure-sensitive adhesive layer are laminated in this order.
  • the energy ray-curable pressure-sensitive adhesive When the energy ray-curable pressure-sensitive adhesive is cured, at least part of the energy ray-polymerizable groups contained in the anchor coat layer are also polymerized to form a covalent bond between a part of the pressure-sensitive adhesive layer and the anchor coat layer, It is speculated that the pressure-sensitive adhesive layer and the base material can maintain close contact through the anchor coat layer.
  • the adhesive sheet described in Patent Document 1 is specifically an adhesive sheet for protecting the circuit surface of a semiconductor wafer when grinding the back surface of the semiconductor wafer. It is said that this adhesive sheet can also be used for temporarily fixing a wafer in the dicing process of a semiconductor wafer. could cause the following problems.
  • the dicing tape is applied to the dicing process while being attached to the ring frame. In the dicing process, washing water is sprayed to cool the frictional heat generated between the dicing blade rotating at high speed and the glass substrate or sapphire glass substrate, and to remove chips, but it can withstand the load and water pressure.
  • the dicing tape must adhere firmly to the ring frame.
  • the dicing tape since the dicing tape may be expanded as necessary, it is necessary to firmly adhere the dicing tape to the ring frame so as not to separate from the ring frame.
  • the adhesive strength of the part irradiated with active energy rays is reduced, so the part attached to the ring frame (paste margin) will not stick.
  • the agent layer is normally not irradiated with active energy rays to maintain high adhesive strength.
  • Patent Document 2 for the purpose of providing a pressure-sensitive adhesive sheet for glass substrate dicing, which can obtain cut pieces with excellent shape properties and which is less likely to cause chipping or chip flying in the cut pieces, a thickness of 130 ⁇ m or more, Also disclosed is a pressure-sensitive adhesive sheet for glass substrate dicing, comprising a base film having a tensile modulus of elasticity of 1 GPa or more and a pressure-sensitive adhesive layer having a thickness of 9 ⁇ m or less provided on the base film.
  • an ultraviolet curable pressure-sensitive adhesive sheet is exemplified in which a polyester film (tensile modulus of elasticity 1.5 GPa) having one surface subjected to corona treatment is used as the base film, and an ultraviolet curable pressure-sensitive adhesive layer is formed. .
  • the adhesive sheet of Patent Document 2 is an adhesive sheet for dicing a glass substrate, but there is no description of adhesive residue on the ring frame, and as described above, the unnecessary dicing tape was peeled off from the ring frame after the dicing process. Sometimes, it was unclear whether the adhesive layer would transfer (adhesive residue) to the ring frame, and there was a concern that adhesive residue would occur. Further, when the adhesive sheet of Patent Document 2 is used as a back grinding tape for semiconductor wafers, the following problems may occur. That is, when the back grind tape is peeled off after the required steps, the substrate film and the ultraviolet curable adhesive layer are peeled off from the entire surface of the semiconductor wafer, which has unevenness due to circuit formation on the surface and has a large area.
  • the load applied to the interface is large, and there is a concern that the UV-curable adhesive layer may be interfacially peeled from the base film, and the UV-curable adhesive may be transferred to the surface of the semiconductor wafer.
  • the thickness of the adhesive is relatively thin, and it becomes difficult to follow the circuit formed on the surface of the semiconductor wafer, and it cannot be sufficiently protected.
  • water may enter the interface between the semiconductor wafer and the adhesive layer.
  • after grinding when irradiated with active energy rays, it is susceptible to oxygen inhibition, and the UV-curable adhesive layer cannot be sufficiently cured, so that the unnecessary backgrinding tape is peeled off from the entire surface of the semiconductor wafer. There is also a possibility that adhesive residue may remain on the peripheral edge of the circuit surface.
  • JP 2013-23665 A Japanese Unexamined Patent Application Publication No. 2004-10829
  • the present invention has been made in view of the above problems and circumstances.
  • Adhesion to the curable adhesive is sufficiently high both before and after irradiation with active energy rays, and even when used as a back grind tape for ultra-thin semiconductor wafers, when peeled off
  • the active energy ray-curable adhesive layer can be peeled off without being transferred to the semiconductor wafer.
  • An object of the present invention is to provide an adhesive tape for work processing.
  • the pressure-sensitive adhesive tape for work processing of the present invention comprises a base film made of a polyester resin composition, an intermediate layer, and an active energy ray-curable pressure-sensitive adhesive layer in this order
  • the intermediate layer is made of a resin composition containing a ternary or higher (meth)acrylic acid ester copolymer (A1) containing methyl acrylate (MA) and methacrylic acid (MAA) as copolymer monomer components,
  • A1 a ternary or higher (meth)acrylic acid ester copolymer
  • MAA methacrylic acid
  • a photosensitive carbon-carbon double bond is introduced into the side chain of a (meth)acrylic acid ester copolymer base polymer (BP) having two or more elements (meta).
  • the binary (meth)acrylic acid ester copolymer base polymer (BP) is 100 mass based on the total amount of copolymer monomer components constituting the (meth)acrylic acid ester copolymer base polymer (BP) When expressed as parts, it is characterized by containing n-butyl acrylate (n-BA) as a copolymer monomer component at a ratio of more than 50 parts by mass and not more than 90 parts by mass.
  • the ternary or higher (meth)acrylic acid ester copolymer (A1) contains acrylic acid as a copolymer monomer component other than the methyl acrylate (MA) and methacrylic acid (MAA). It is a tertiary or higher (meth)acrylic acid ester copolymer containing 2-ethylhexyl (2-EHA).
  • the ternary or higher (meth)acrylate copolymer (A1) comprises 2-ethylhexyl acrylate (2-EHA), methyl acrylate (MA) and methacrylic acid (MAA).
  • Ternary (meth)acrylic acid ester copolymer as a copolymer monomer component 100 parts by mass based on the total amount of copolymer monomer components constituting the ternary (meth)acrylic acid ester copolymer
  • the 2-ethylhexyl acrylate (2-EHA) is in the range of 26 parts by mass or more and 51 parts by mass or less
  • the methyl acrylate (MA) is in the range of 47 parts by mass or more and 67 parts by mass or less
  • methacrylic acid (MAA ) is in the range of 2 parts by mass or more and 7 parts by mass or less, and is adjusted so that the total amount of the copolymer monomer component is 100 parts by mass.
  • the ternary or higher (meth)acrylic acid ester copolymer (A1) has a glass transition temperature (Tg) in the range of -36°C or higher and -9°C or lower.
  • the binary (meth)acrylic acid ester copolymer base polymer (BP) comprises n-butyl acrylate (n-BA) and 2-hydroxyethyl acrylate (2-HEA).
  • n-BA n-butyl acrylate
  • 2-HEA 2-hydroxyethyl acrylate
  • a ternary (meth)acrylic acid ester copolymer containing methacrylic acid (MAA) as a copolymer monomer component, and a copolymer monomer constituting the (meth)acrylic acid ester copolymer base polymer (BP) When the total amount of the components is 100 parts by mass as a reference, the n-butyl acrylate (n-BA) in the range of 66 parts by mass or more and 90 parts by mass or less, and the 2-hydroxyethyl acrylate (2-HEA) in the range of 9.
  • the methacrylic acid (MAA) in the range of 0.2 parts by mass or more and 3 parts by mass or less, adjusted so that the total amount of the monomer components of the copolymer is 100 parts by mass. .
  • the binary or higher (meth)acrylate copolymer base polymer has a glass transition temperature (Tg) in the range of -50°C or higher and -39°C or lower.
  • the intermediate layer has a thickness of 5 ⁇ m or more.
  • the active energy ray-curable pressure-sensitive adhesive layer has a thickness of 5 ⁇ m or more.
  • the sum of the thickness of the intermediate layer and the thickness of the active energy ray-curable pressure-sensitive adhesive layer is 10 ⁇ m or more.
  • the base film made of the polyester resin composition is a polyethylene terephthalate film.
  • the adhesive strength of the adhesive tape for work processing to a glass plate before ultraviolet irradiation is in the range of 5.0 N/25 mm or more and 25.0 N/25 mm or less, and the adhesive strength after ultraviolet irradiation is 0. 01 N/25 mm or more and 0.50 N/25 mm or less.
  • the adhesive force of the adhesive tape for work processing to a stainless steel plate (SUS304BA plate) before ultraviolet irradiation is in the range of 5.0 N/25 mm or more and 25.0 N/25 mm or less, and the adhesive strength after ultraviolet irradiation The force ranges from 0.01 N/25 mm to 0.50 N/25 mm.
  • the base film and the active energy ray-curable pressure-sensitive adhesive layer are used as the pressure-sensitive adhesive layer, the base film and the active energy ray-curable pressure-sensitive adhesive
  • the adhesion of the active energy ray is sufficiently large both before and after the irradiation of the active energy ray, and even when used as a back grind tape for ultra-thin semiconductor wafers, the active energy ray curable type
  • the adhesive layer can be peeled off without being transferred to the semiconductor wafer, and even when used as a dicing tape for cutting a fragile work such as a glass substrate or a hard work such as a sapphire glass substrate, the process It is possible to provide an adhesive tape for work processing which is not peeled off from a ring frame inside and which can be peeled off without leaving an adhesive residue when peeled off from the ring frame.
  • the present invention provides a work processing adhesive tape that can be used as a backgrinding tape that can handle the grinding and ultra-thinning of semiconductor wafers, and that can also be used as a dicing tape that can handle fragile works such as glass substrates. be able to.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of a work processing pressure-sensitive adhesive tape to which the present embodiment is applied
  • FIG. 4 is a cross-sectional view showing an example of another aspect of the configuration of the pressure-sensitive adhesive tape for work processing to which the present embodiment is applied
  • a state in which a ring frame (wafering) is attached to the outer edge of the adhesive tape for workpiece processing to which the present embodiment is applied, and a glass substrate separated into individual pieces by a dicing process is adhered and held to the central portion of the adhesive tape for workpiece processing. is a perspective view showing the from above.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of a work processing pressure-sensitive adhesive tape to which the present embodiment is applied
  • FIG. 4 is a cross-sectional view showing an example of another aspect of the configuration of the pressure-sensitive adhesive tape for work processing to which the present embodiment is applied
  • FIG. 3 is a schematic cross-sectional view showing a mode of using the work processing adhesive tape to which the present embodiment is applied in a dicing process
  • FIG. 4 is a perspective view showing from below a state in which the work processing adhesive tape to which the present embodiment is applied is peeled off from the ring frame
  • BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic sectional drawing which showed the aspect which uses the adhesive tape for a workpiece
  • FIG. 1 is a cross-sectional view showing an example of the configuration of a work processing adhesive tape to which the present embodiment is applied.
  • a work processing pressure-sensitive adhesive tape 10 has a configuration in which an intermediate layer 2 and an active energy ray-curable pressure-sensitive adhesive layer 3 are provided on one surface of a base film 1 in this order.
  • the surface of the active energy ray-curable adhesive layer 3 of the work processing adhesive tape 10 (the surface opposite to the surface facing the base film 1) is coated with a release agent.
  • a material sheet (release liner) may be provided.
  • the base film 1 is composed of a polyester-based resin composition.
  • the intermediate layer 2 is formed from a resin composition containing a predetermined (meth)acrylate copolymer.
  • the active energy ray-curable pressure-sensitive adhesive layer 3 is a (meth)acrylic acid in which a photosensitive carbon-carbon double bond is introduced into the side chain of a predetermined (meth)acrylic acid ester copolymer base polymer (BP). It is formed from an adhesive composition containing an ester copolymer.
  • FIG. 2 is a cross-sectional view showing an example of another aspect of the configuration of the work processing pressure-sensitive adhesive tape to which the present embodiment is applied.
  • the work processing pressure-sensitive adhesive tape 10 has a configuration in which an intermediate layer 2 and an active energy ray-curable pressure-sensitive adhesive layer 3 are provided in this order on one surface of a base film 1.
  • the substrate film 1 in FIG. 1 has a single layer structure
  • the substrate film 1 in FIG. It has a laminated structure of a resin layer 1b composed of materials.
  • Other configurations are the same as those in FIG.
  • the work processing adhesive tape 10 having such a structure cuts and separates hard works such as brittle and fragile glass substrates, crystal substrates, sapphire glass substrates, etc., which have undergone various circuit formations or surface treatments, for example, into small pieces. Used in the dicing process. It can also be used in the dicing process of ordinary silicon semiconductor wafers and compound semiconductor wafers such as silicon carbide, gallium arsenide, gallium phosphide, and gallium nitride. Specifically, it is used as a dicing tape as shown in FIGS. 3 and 4. FIG.
  • the activity of the central portion of the work processing adhesive tape 10 was applied.
  • a glass substrate 30 for example, is attached to the energy ray-curable pressure-sensitive adhesive layer 3 so that the side on which no circuit is formed is in contact with the active energy ray-curable pressure-sensitive adhesive layer 3 .
  • the thickness of the work such as a glass substrate, a crystal substrate, or a sapphire glass substrate is, for example, in the range of 50 ⁇ m or more and 5000 ⁇ m or less.
  • the glass substrate 30 is cut into glass chips 30a of a predetermined size by a dicing blade 40 rotating at high speed while spraying cleaning cooling water.
  • the planar area of the chip is, for example, in the range of 1 ⁇ 10 ⁇ 6 mm 2 to 9 mm 2 .
  • active energy rays such as ultraviolet rays (UV) are irradiated from the base film 1 side of the adhesive tape 10 for work processing to the active energy ray-curable adhesive layer 3 portion where the work is bonded, and the active energy ray-curable adhesive layer 3 is irradiated.
  • UV ultraviolet rays
  • the adhesive force of the adhesive layer 3 is lowered, and the glass chip 30 a is picked up (peeled off) from the active energy ray-curable adhesive layer 3 of the adhesive tape 10 for work processing. Thereby, a high-quality glass chip 30a in which chipping is suppressed can be obtained.
  • FIG. 5 is a bottom perspective view showing a state in which the unnecessary workpiece processing adhesive tape 10 is peeled off from the ring frame 20 after all the glass chips 30a have been picked up.
  • the adhesive tape for work processing is peeled off from the ring frame manually, but may be peeled off using a peeling device or the like.
  • the ring frame 20 from which the work processing adhesive tape 10 has been peeled off is washed and reused as necessary. If the adhesive layer of the adhesive layer peels off from the base film 1 and is transferred (adhesive residue), it takes time to wash, and the working efficiency is lowered.
  • the work processing adhesive tape 10 having such a configuration can also be used in a back grinding process for grinding semiconductor wafers such as silicon wafers, which have been subjected to various circuit formations or other surface processing, to an extremely thin thickness. can. Specifically, it is used as a back grind tape as shown in FIG. First, as shown in FIG. 6A, the active energy ray-curable adhesive layer 3 side of the work processing adhesive tape 10 is placed on the surface of the semiconductor wafer 50 having a thickness of, for example, 775 ⁇ m, on which the circuits 51 are formed. to paste together.
  • FIG. 6(b) shows a state in which the semiconductor wafer 50' is held by the workpiece processing adhesive tape 10 after the grinding of the semiconductor wafer 50 is finished and the semiconductor wafer 50' is thinned to a predetermined thickness.
  • the thickness of the thinned semiconductor wafer 50' is, for example, in the range of 20 ⁇ m or more and 100 ⁇ m or less.
  • active energy ray-curable adhesive layer 3 is laminated with a semiconductor wafer 50' thinned with active energy rays such as ultraviolet rays (UV). to cure the active energy ray-curable pressure-sensitive adhesive layer 3 and reduce its adhesive strength.
  • active energy rays such as ultraviolet rays (UV).
  • UV ultraviolet rays
  • FIG. 7(a) a ring frame 20 made of SUS is attached to the active energy ray-curable adhesive layer 3 on the outer edge of a separately prepared dicing tape 11 punched out into a circular shape, and then diced.
  • the ground surface side of the thinned semiconductor wafer 50 ′ is attached to the active energy ray-curable adhesive layer 3 at the central portion of the tape 11 so that the active energy ray-curable adhesive layer 3 is in contact with the ground surface side.
  • a strip-shaped peeling tape 12 (for example, 50 mm wide by 60 mm long) is adhered to the back surface of the base film 1 of the adhesive tape 10 for work processing by pressure bonding or thermocompression bonding.
  • the workpiece processing adhesive tape 10 has substantially the same shape as the thin-film semiconductor wafer 50' and does not have a starting point for peeling. Then, before performing the dicing process of the next process, as shown in FIG. Peel off from the surface of 50'.
  • the peeling is performed manually or by using a peeling device or the like.
  • the thinned semiconductor wafer 50 ′ is held by suction on a holding table (not shown) via the dicing tape 11 .
  • a holding table not shown
  • the base film 1 in the work processing pressure-sensitive adhesive tape 10 of the present embodiment will be described below.
  • the base film 1 a film made of a polyester-based resin composition is used from the viewpoint of tensile strength and rigidity.
  • the film made of the polyester-based resin composition is a film mainly composed of polyester, and the polyester is the entire resin component in the resin composition constituting the base film 1 (additives other than resin from the resin composition
  • the content is preferably 70% by mass or more, and more preferably 80% by mass or more, which has a composition close to that of polyester alone, relative to the components except for ).
  • the upper limit is not particularly limited, and is 100% by mass or less.
  • polyesters that is the main component of the base film 1 include crystalline linear saturated polyester obtained by polycondensation of an aromatic dibasic acid or an ester derivative thereof and a diol or an ester derivative thereof. be done.
  • polyesters include homopolyesters such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate, and copolymerized polyesters containing these resin components as main components. mentioned.
  • the above polyesters can be used by blending the above homopolyesters, or by blending the above homopolyesters with the above copolyesters.
  • polyethylene terephthalate is particularly preferable because it is easily available, has good mechanical strength (tensile strength, rigidity, etc.), good transparency and heat resistance, and is easy to obtain the substrate film 1 with high thickness accuracy.
  • Examples of the aromatic dibasic acid of the homopolyester include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the diol include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, and the like. are mentioned.
  • the repeating unit of the homopolyester that is, the total amount of the main repeating units composed of the aromatic dibasic acid component and the diol component is preferably 80 mol% or more of all the repeating units, and is 90 mol% or more. is more preferable, and 95 mol % or more is even more preferable.
  • aromatic dibasic acid of the copolymer polyester examples include oxycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and paraoxybenzoic acid. etc., and these can be used alone or in combination of two or more.
  • oxycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and paraoxybenzoic acid. etc., and these can be used alone or in combination of two or more.
  • diol of the copolymer polyester examples include ethylene glycol, diethylene glycol, 1,4-butanediol, propylene glycol, neopentyl glycol, etc. These may be used alone or in combination of two or more. be able to.
  • the mass ratio of the copolymerization component of the copolymer polyester is preferably less than 20% by mass. When the mass ratio is less than 20% by mass, the mechanical strength, transparency, heat resistance, and thickness accuracy of the base film 1 can be maintained.
  • the polyester is preferably contained in a proportion of 70% by mass or more relative to the total resin components (components excluding additives other than resins from the resin composition) constituting the base film 1, but the resin
  • the component may optionally include other resins other than the polyester, such as aromatic ether compounds, ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, polyolefin-based elastomers, polyamide-based Elastomers, polycarbonate resins, ionomer resins and the like can be contained.
  • the other resins have mechanical strength, transparency, and heat resistance of the base film 1 with respect to the entire resin component (the resin composition excluding additives other than the resin) that constitutes the base film 1. From the viewpoint of maintaining thickness accuracy, it is preferably contained at a rate of 30% by mass or less, more preferably at a rate of 20% by mass or less.
  • polyester/polyether block type thermoplastic elastomer in which an aromatic polyester is used for the hard segment and a polyether is used for the soft segment
  • a so-called polyester/polyester block type thermoplastic elastomer using an aromatic polyester for the hard segment and an aliphatic polyester for the soft segment can also be exemplified.
  • polyester/polyether block type thermoplastic elastomers include thermoplastic polyester elastomers using polybutylene terephthalate as the hard segment polyester and polytetramethylene ether glycol as the soft segment polyether.
  • polyester/polyester block type thermoplastic elastomers include thermoplastic polyester elastomers using polybutylene terephthalate as the hard segment polyester and polylactone as the soft segment polyester.
  • the polyester-based resin composition that constitutes the base film 1 preferably contains particles for the main purpose of imparting lubricity to the base film 1 .
  • the type of particles to be blended is not particularly limited as long as they are particles capable of imparting lubricity. Specific examples include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid. Examples include inorganic particles such as magnesium, kaolin, aluminum oxide, and titanium oxide, and heat-resistant organic particles such as thermosetting urea resin, thermosetting phenol resin, thermosetting epoxy resin, and benzoguanamine resin.
  • the shape of the particles to be used is not particularly limited, and any of spherical, massive, rod-like, flattened and the like may be used. Two or more kinds of these series of particles may be used in combination, if necessary.
  • the length average particle diameter of the particles is usually in the range of 0.01 ⁇ m to 3 ⁇ m, preferably 0.01 ⁇ m to 1 ⁇ m.
  • the substrate film 1 can be provided with appropriate slipperiness and smoothness.
  • the content of the particles is usually in the range of 0.001% by mass to 5% by mass, preferably 0.005% by mass to 3% by mass, with respect to the entire resin component constituting the base film 1. be. When the content of the particles is within the above range, appropriate lubricity and smoothness can be imparted.
  • the polyester-based resin composition in addition to the particles described above, may optionally include conventionally known catalysts, antioxidants, antistatic agents, heat stabilizers, lubricants, and dyes, as long as the effects of the present invention are not impaired. , pigments and the like can be added.
  • any of non-stretched polyester film, uniaxially stretched polyester film, and biaxially stretched polyester film can be used as the base film 1 made of the above polyester resin composition, but biaxially stretched polyester film is preferred. Specifically, a biaxially stretched polyethylene terephthalate film is preferred.
  • the base film 1 may have a single-layer structure, or may have a laminated structure of two or more layers. From the viewpoint of simplification of the process and thickness accuracy, the base film 1 preferably has a single-layer structure as shown in FIG. When the substrate film 1 has a two-layer structure, for example, as shown in FIG. It has a laminated structure.
  • the resin layer 1a is a layer on the side that is in direct contact with the intermediate layer 2, and when the base film 1 has a laminated structure, at least the resin layer 1a that is in direct contact with the intermediate layer 2 is the polyester-based Consists of a resin composition.
  • the resin layer 1b may be a layer composed of a resin composition other than polyester, or may be a layer composed of a polyester-based resin composition.
  • the resin component of the resin composition other than polyester the same resin as the resin exemplified above as the resin other than polyester can be used.
  • the total thickness of the base film 1 is not particularly limited as long as it can be formed as a film.
  • the range is as follows. If the total thickness of the base film 1 is less than 12 ⁇ m, the work processing adhesive tape 10 becomes difficult to handle during manufacturing or use in the process. The quality of the semiconductor wafer 50', etc., which has been processed may be deteriorated. On the other hand, if the total thickness exceeds 250 ⁇ m, the rigidity becomes too high, and as a result, the quality of the processed work may deteriorate.
  • the total thickness of the layers composed of the polyester-based resin composition depends on the total thickness of the base film 1 as a whole. Although it cannot be said, for example, it is preferable to set the thickness to a ratio of 50% or more of the total thickness of the base film 1 as a whole. If the above ratio is 50%, the quality of the machined work will be good.
  • the intermediate layer 2 in the work processing pressure-sensitive adhesive tape 10 of the present embodiment will be described below.
  • the intermediate layer 2 is a ternary or higher (meth)acrylate copolymer (A1) containing methyl acrylate (MA) and methacrylic acid (MAA) as copolymer monomer components (hereinafter simply “(meth) (sometimes referred to as “acrylic acid ester copolymer (A1)”), and the copolymer monomer component constituting the ternary or higher (meth)acrylic acid ester copolymer (A1)
  • the total amount is 100 parts by mass as a reference
  • at least the methyl acrylate (MA) is included in the range of 47 parts by mass to 67 parts by mass
  • the methacrylic acid (MAA) is included in the range of 2 parts by mass to 7 parts by mass. Including in the range.
  • the content of the ternary or higher (meth)acrylic acid copolymer (A) with respect to the total amount of the resin composition
  • the ternary or higher (meth)acrylic acid ester copolymer (A1) is a copolymer monomer component other than the methyl acrylate (MA) and methacrylic acid (MAA), the (meth)acrylic acid ester
  • MAA methyl acrylate
  • MAA methacrylic acid
  • the total amount of the copolymer monomer components constituting the copolymer (A1) is taken as the standard 100 parts by mass, it is included in the range of 26 parts by mass or more and 51 parts by mass or less.
  • the copolymer monomer component other than the methyl acrylate (MA) and methacrylic acid (MAA) is not particularly limited as long as it is a monomer that can be copolymerized with the methyl acrylate (MA) and methacrylic acid (MAA).
  • These monomers can be used alone or in combination of two or more.
  • the (meth)acrylic acid ester monomer having a linear or branched alkyl group having 2 to 20 carbon atoms include ethyl (meth)acrylate, propyl (meth)acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) ) isopentyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, ( Decyl (meth) acrylate, isodecyl (meth) acrylate,
  • the carbon number is 2 or more and 8 or less.
  • (Meth)acrylic acid ester monomers having a linear or branched alkyl group are preferred, specifically ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl and the like are preferably used.
  • (meth)acrylic acid cycloalkyl ester monomers include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.
  • the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; Acid anhydride monomers such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 6 -Hydroxy such as hydroxyhexyl, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc.
  • carboxyl group-containing monomers such as acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate,
  • Group-containing monomer styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid, etc.
  • sulfonic acid group-containing monomer phosphoric acid group-containing monomer such as 2-hydroxyethyl acryloyl phosphate; glycidyl group-containing monomer such as (meth)acrylic acid glycidyl ester; (meth)acrylic acid amide, (meth)acrylic acid N-hydroxy amide group-containing monomers such as methylamide; and amino group-containing monomers such as alkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and t-butylaminoethyl (meth)acrylate.
  • phosphoric acid group-containing monomer such as 2-hydroxyethyl acryloyl phosphate
  • glycidyl group-containing monomer such as (meth)acrylic acid glycidyl ester
  • (meth)acrylic acid amide, (meth)acrylic acid N-hydroxy amide group-containing monomers such as methylamide
  • adhesion between the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3 adhesion between the intermediate layer 2 and the base film 1, and improvement of the cohesion of the intermediate layer 2
  • Acrylic acid, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylamide and the like are preferably used.
  • ternary or higher (meth)acrylic acid ester copolymer (A1) in the present invention acrylic acid It is preferable to use a tertiary or higher (meth)acrylic acid ester copolymer containing 2-ethylhexyl (2-EHA) as a copolymer monomer component.
  • ternary or higher (meth)acrylic acid ester copolymers include: (1) a terpolymer of 2-ethylhexyl acrylate (2-EHA), methyl acrylate (MA) and methacrylic acid (MAA); (2) a tetrapolymer of 2-ethylhexyl acrylate (2-EHA), n-butyl acrylate (n-BA), methyl acrylate (MA) and methacrylic acid (MAA); (3) a tetrapolymer of 2-ethylhexyl acrylate (2-EHA), methyl acrylate (MA), 2-hydroxyethyl acrylate (2-HEA) and methacrylic acid (MAA); (4) a tetrapolymer of 2-ethylhexyl acrylate (2-EHA), methyl acrylate (MA), ethyl acrylate (EA) and methacrylic acid (MAA); (5) Quaternary copo
  • a copolymer or a terpolymer of n-butyl acrylate (n-BA), methyl acrylate (MA) and methacrylic acid (MAA) can be preferably used, and 2-ethylhexyl acrylate (2- EHA), methyl acrylate (MA), and methacrylic acid (MAA) are more preferably used as ternary (meth)acrylic acid ester copolymers.
  • each monomer component contains acrylic acid when the total amount of the copolymer monomer components constituting the ternary (meth)acrylic acid ester copolymer is set to 100 parts by mass based on 2-ethylhexyl (2-EHA) in the range of 26 parts by mass to 51 parts by mass, methyl acrylate (MA) in the range of 47 parts by mass to 67 parts by mass, and methacrylic acid (MAA) in the range of 2 parts by mass to 7 parts by mass. It is preferable that the total amount of the copolymer monomer component is adjusted to 100 parts by mass within the range of 100 parts by mass or less.
  • the ternary or higher (meth)acrylic acid ester copolymer (A1) is one selected from the methyl acrylate (MA) monomer, the methacrylic acid (MAA) monomer, and the above-described monomers other than these two monomers. Alternatively, it can be obtained by polymerizing a mixture of two or more monomers in predetermined amounts as copolymer monomer components. Polymerization can be carried out by any method such as solution polymerization, emulsion polymerization, bulk polymerization and suspension polymerization.
  • the weight-average molecular weight (Mw) of the ternary or higher (meth)acrylic acid ester copolymer (A1) is preferably 100,000 or more from the viewpoint of improving the cohesion of the intermediate layer 2.
  • the weight average molecular weight (Mw) is preferably in the range of 100,000 to 1,500,000, more preferably in the range of 300,000 to 1,000,000.
  • the weight average molecular weight (Mw) is the weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography (GPC).
  • the glass transition temperature (Tg) of the ternary or higher (meth)acrylic acid ester copolymer (A1) is not particularly limited as long as it does not interfere with the effects of the present invention. 1 and the intermediate layer 2, the adhesiveness between the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3 described later, and the processing quality of the workpiece, the temperature at -36 ° C. or higher and -9 ° C. or lower It is preferably in the range of ⁇ 36° C. or higher and ⁇ 18° C. or lower, more preferably.
  • the glass transition temperature (Tg) is determined based on the composition of the monomer components constituting the ternary or higher (meth)acrylic acid ester copolymer (A1), and the Fox formula shown in the following general formula (1): It is a theoretical value calculated by
  • Tg is the glass transition temperature (unit: K) of the ternary or higher (meth)acrylic acid ester copolymer (A1)
  • the glass transition temperature (Tg) of homopolymers can be found, for example, in "Polymer Handbook” (edited by J. Brandrup and EH Immergut, Interscience Publishers).
  • the glass transition temperature (Tg) is within the above range, for example, when a brittle and fragile work such as a glass substrate 30 is diced with a rotating dicing blade 40, the work on the adhesive layer 3 is held well. , is fixed, and furthermore rocking can be suppressed, so that chipping and dimensional and positional deviation of the chip can be suppressed.
  • steps such as the circuits 51 and electrodes on the surface of the semiconductor wafer 50.
  • the acid value of the ternary or higher (meth)acrylic acid ester copolymer (A1) is not particularly limited as long as it does not interfere with the effects of the present invention. From the viewpoint of adhesion with the layer 2, adhesion between the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3 described later, and improvement of the cohesive strength of the intermediate layer 2, it is preferable that it is 13.0 mgKOH/g or more.
  • suppression of gelation during polymerization of the copolymer (A1) and rigidity of the intermediate layer 2 (decrease in the adhesive strength of the adhesive tape 10 for work processing before irradiation with active energy rays and deterioration in step followability due to increased rigidity) from the point of view, it is preferably 50.7 mgKOH/g or less. That is, the acid value is preferably in the range of 13.0 mgKOH/g or more and 50.7 mgKOH/g or less.
  • the hydroxyl value of the ternary or higher (meth)acrylic acid ester copolymer (A1) is not particularly limited as long as it does not interfere with the effects of the present invention.
  • Adhesion with the intermediate layer 2, adhesion between the intermediate layer 2 and the active energy ray-curable adhesive layer 3 described later, and rigidity of the intermediate layer 2 (active energy ray irradiation of the adhesive tape 10 for work processing due to increased rigidity From the viewpoint of reduction in front adhesive strength and reduction in conformability to irregularities), it is preferably in the range of 0 mgKOH/g or more and 96.6 mgKOH/g or less.
  • the resin composition constituting the intermediate layer 2 is crosslinked so as to react with the functional group of the ternary or higher (meth)acrylic acid ester copolymer (A1). It is preferable to contain an agent.
  • a cross-linking agent is not particularly limited, and is a functional group possessed by the ternary or higher (meth)acrylic acid ester copolymer (A1), that is, a carboxyl group, or a hydroxy group introduced as necessary, A known cross-linking agent having a functional group capable of reacting with a glycidyl group or the like can be used.
  • polyisocyanate-based cross-linking agents for example, polyisocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, aziridine-based cross-linking agents, melamine resin-based cross-linking agents, urea resin-based cross-linking agents, acid anhydride compound-based cross-linking agents, and polyamine-based cross-linking agents
  • Cross-linking agents, carboxyl group-containing polymer-based cross-linking agents, and the like can be mentioned.
  • These cross-linking agents may be used alone or in combination of two or more.
  • the amount of the cross-linking agent is in the range of 0.01 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the solid content of the ternary or higher (meth)acrylate copolymer (A1). More preferably, it is in the range of 0.1 parts by mass or more and 5.0 parts by mass or less.
  • polyisocyanate-based cross-linking agent examples include polyisocyanate compounds having an isocyanurate ring, adduct polyisocyanate compounds obtained by reacting trimethylolpropane and hexamethylene diisocyanate, and adducts obtained by reacting trimethylolpropane and tolylene diisocyanate.
  • examples include polyisocyanate compounds, adduct polyisocyanate compounds obtained by reacting trimethylolpropane and xylylene diisocyanate, and adduct polyisocyanate compounds obtained by reacting trimethylolpropane and isophorone diisocyanate. These can be used singly or in combination of two or more.
  • epoxy-based cross-linking agent examples include bisphenol A/epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether.
  • trimethylolpropane triglycidyl ether trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidylerythritol, diglycerol polyglycidyl ether, 1,3′-bis(N,N-diglycidylaminomethyl)cyclohexane, N , N,N',N'-tetraglycidyl-m-xylenediamine and the like. These can be used singly or in combination of two or more.
  • the thickness of the intermediate layer 2 may be appropriately adjusted according to the processing of the workpiece, but is not particularly limited as long as it does not impair the effects of the present invention. and the adhesion between the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3 described later, for example, it is preferably 5 ⁇ m or more, and the coating of the solution of the resin composition of the intermediate layer 2 - It is preferable that it is 150 micrometers or less from a viewpoint of drying suitability. That is, the thickness of the intermediate layer 2 is preferably in the range of 5 ⁇ m to 150 ⁇ m, more preferably in the range of 5 ⁇ m to 100 ⁇ m.
  • the active energy ray-curable adhesive layer 3 (hereinafter sometimes simply referred to as "adhesive layer 3") in the work processing adhesive tape 10 of the present embodiment will be described below.
  • a photosensitive carbon-carbon double bond is introduced into the side chain of a (meth)acrylic acid ester copolymer base polymer (BP) having two or more elements (meth ) acrylic acid ester copolymer (A2) (hereinafter sometimes simply referred to as “(meth)acrylic acid ester copolymer (A2)”) and a pressure-sensitive adhesive composition containing a cross-linking agent.
  • the content ratio of the (meth)acrylic acid ester copolymer (A2) to the total amount of the pressure-sensitive adhesive composition is preferably 90% by mass or more, more preferably 95% by mass or more.
  • the method for producing the (meth)acrylic acid ester copolymer (A2) in which a photosensitive carbon-carbon double bond is introduced in the side chain is not particularly limited, but usually (meth) ) A copolymer monomer component containing an acrylic acid ester monomer and a functional group-containing monomer is copolymerized to obtain a (meth)acrylic acid ester copolymer base polymer, and the functional group possessed by the base polymer undergoes an addition reaction. and a method of subjecting a compound having a carbon-carbon double bond (active energy ray-reactive compound) to an addition reaction.
  • the (meth)acrylic acid ester copolymer base polymer (BP) (hereinafter sometimes simply referred to as base polymer (BP)) of two or more elements in the present embodiment is the (meth)acrylic acid ester copolymer
  • base polymer (BP) base polymer
  • n-butyl acrylate (n-BA) as a copolymer monomer component exceeds 50 parts by mass and 90 parts by mass Included in the following proportions.
  • n-butyl acrylate (n-BA) is used as a copolymer monomer component, and the base polymer (BP ) in a ratio of more than 50 parts by mass to 90 parts by mass or less when the total amount of the copolymer monomer component constituting the Adhesion can be made good, and the adhesion can be sufficiently maintained at a level that does not hinder work processing before and after the active energy ray irradiation of the adhesive tape 10 for work processing. can be done.
  • the work processing adhesive tape 10 required to hold the work during processing has a high adhesive strength before the active energy ray irradiation, and the work processing adhesive tape 10 is peeled off from the processed work. It is possible to impart cohesive force to the pressure-sensitive adhesive layer 3 necessary for suppressing adhesive residue on the work when applying. As a result, the quality of the machined work can be improved.
  • the total amount of the copolymer monomer component constituting the base polymer (BP) is set to 100 parts by mass based on the binary or higher (meth)acrylic acid ester copolymer base polymer (BP), the acrylic As a copolymer monomer component other than n-butyl acid (n-BA), 10 parts by mass or more and 34 parts by mass or less of a functional group-containing monomer, and other copolymer monomers (excluding n-BA and functional group-containing monomers) It is preferable that the total amount of the copolymer monomer component is adjusted to 100 parts by mass at a ratio of 0 parts by mass or more and less than 40 parts by mass.
  • Examples of the functional group-containing monomer include the same carboxyl group-containing monomers and acid anhydrides as the functional group-containing monomer components of the ternary or higher (meth)acrylic acid ester copolymer (A1) of the intermediate layer 2 described above.
  • monomers, hydroxyl group-containing monomers, sulfonic acid group-containing monomers, glycidyl group-containing monomers, amide group-containing monomers, amino group-containing monomers, and the like can be used singly or in combination of two or more. Among these, it is preferable to use a hydroxy group-containing monomer from the viewpoint of ease of addition reaction with the active energy ray-reactive compound described below.
  • hydroxy group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxy(meth)acrylate. hydroxyhexyl, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate and the like. .
  • 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred from the viewpoint of versatility.
  • the purpose of copolymerizing the functional group-containing monomer is, first, to the binary or higher (meth)acrylic acid ester copolymer base polymer (BP), the functional group is subjected to the active energy ray reaction described later. Secondly, the above (meth)acrylic acid ester copolymer (A2) is reacted with a cross-linking agent described later to obtain a high molecular weight Third, in order to make it an active point (polar point) for improving the initial adhesion between the active energy ray-curable pressure-sensitive adhesive layer 3 and the work after the crosslinking reaction, Fourth, the active point (polar point) for improving the adhesion between the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3, the content ratio of the functional group-containing monomer is the above-mentioned is adjusted in the range of 10% by mass or more and 34% by mass or less with respect to the total amount of copolymer monomer components constituting the binary or higher (meth)acrylic acid ester copoly
  • the binary or higher (meth)acrylic acid copolymer base polymer (BP) is used as a copolymer monomer component.
  • other copolymer monomers excluding n-BA and functional group-containing monomers
  • it can be contained at a rate of less than 40% by mass.
  • the other copolymer monomer component is not particularly limited as long as it is a monomer that can be copolymerized with the n-butyl acrylate (n-BA) and the functional group-containing monomer.
  • the number of carbon atoms is 1 or more.
  • examples thereof include (meth)acrylic acid ester monomers having linear or branched alkyl groups of 20 or less, (meth)acrylic acid cycloalkyl ester monomers, vinyl acetate, styrene, acrylonitrile, N-methylvinylpyrrolidone, and the like. These monomers can be used alone or in combination of two or more.
  • the (meth)acrylic acid ester monomer having a linear or branched alkyl group having 1 to 20 carbon atoms has a linear alkyl group having 1 carbon atom
  • the same copolymer monomer components as those exemplified above for the ternary or higher (meth)acrylic acid ester copolymer (A1) of the intermediate layer 2, i.e., having 2 carbon atoms (Meth)acrylic acid ester monomers having linear or branched alkyl groups of 20 or less.
  • methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, (meth) Stearyl acrylate and the like are preferred.
  • (meth)acrylic acid cycloalkyl ester monomer examples include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.
  • n-butyl acrylate (n-BA) and 2-hydroxyethyl acrylate (2-HEA) are co-polymerized. It is preferable to use a (meth)acrylic acid ester copolymer containing two or more elements as a polymer monomer component.
  • binary or higher (meth)acrylic acid ester copolymers include: (1) a binary copolymer of n-butyl acrylate (n-BA) and 2-hydroxyethyl acrylate (2-HEA); (2) a terpolymer of n-butyl acrylate (n-BA), 2-hydroxyethyl acrylate (2-HEA) and methacrylic acid (MAA); (3) a tetrapolymer of n-butyl acrylate (n-BA), 2-ethylhexyl acrylate (2-EHA), 2-hydroxyethyl acrylate (2-HEA) and methacrylic acid (MAA); (4) Examples include quaternary copolymers of n-butyl acrylate (n-BA), 2-hydroxyethyl acrylate (2-HEA), methyl methacrylate (MMA) and methacrylic acid (MAA).
  • a binary (meth)acrylic acid ester copolymer with n-butyl acrylate (n-BA) and 2-hydroxyethyl acrylate (2-HEA) as copolymer monomer components Polymer or ternary (meth)acrylic acid ester with copolymer monomer components of n-butyl acrylate (n-BA), 2-hydroxyethyl acrylate (2-HEA) and methacrylic acid (MAA)
  • a copolymer can be preferably used, and a ternary copolymer comprising n-butyl acrylate (n-BA), 2-hydroxyethyl acrylate (2-HEA), and methacrylic acid (MAA) as copolymer monomer components
  • a (meth)acrylic acid ester copolymer can be used more preferably.
  • each monomer component is based on 100 parts by mass of the total amount of the copolymer monomer components constituting the ternary (meth) acrylic ester copolymer.
  • n-butyl acid in the range of 66 parts by mass or more and 90 parts by mass or less
  • 2-hydroxyethyl acrylate (2-HEA) in the range of 10 parts by mass or more and 34 parts by mass or less
  • copolymer monomer component It is preferable that the total amount is adjusted to 100 parts by mass.
  • each monomer component is 100 mass based on the total amount of copolymer monomer components constituting the ternary (meth) acrylic acid ester copolymer
  • the range of n-butyl acrylate (n-BA) is 66 parts by mass or more and 90 parts by mass or less
  • the range of 2-hydroxyethyl acrylate (2-HEA) is 9.8 parts by mass or more and 31 parts by mass or less.
  • methacrylic acid (MAA) in the range of 0.2 parts by mass or more and 3 parts by mass or less so that the total amount of the copolymer monomer component is 100 parts by mass.
  • the glass transition temperature (Tg) of the binary or higher (meth)acrylic acid ester copolymer base polymer (BP) is not particularly limited as long as it does not interfere with the effects of the present invention. -50°C or higher and -39°C or lower from the viewpoints of adhesion between the layer 2 and the active energy ray-curable adhesive layer 3, control of the adhesive strength of the adhesive tape for work processing before and after the active energy ray irradiation, and processing quality of the work. is preferably in the range of
  • the glass transition temperature (Tg) is a theoretical value calculated from the Fox formula based on the composition of the monomer components constituting the above binary (meth)acrylic acid ester copolymer base polymer (BP). is.
  • the glass transition temperature (Tg) is within the above range, for example, when dicing a brittle and fragile work such as a glass substrate 30 with a rotating dicing blade 40, the work on the adhesive layer 3 is firmly fixed. Therefore, it is possible to suppress positional deviation of chips and chip flying.
  • the adhesion between the intermediate layer 2 and the adhesive layer 3 described above is improved, adhesive residue on the ring frame 20 and the adhesive layer 3 when the work processing adhesive tape 10 is peeled off from the ring frame 20 after dicing. can be suppressed.
  • steps such as the circuits 51 and electrodes on the surface of the semiconductor wafer 50. ' and transfer of the adhesive layer 3 to the thinned semiconductor wafer 50' can be suppressed.
  • the (meth)acrylic acid ester copolymer (A2) having a photosensitive carbon-carbon double bond introduced into the side chain is obtained by copolymerizing the functional group-containing monomer (meth )
  • a compound having a functional group capable of undergoing an addition reaction with the functional group introduced into the side chain of the acrylic acid ester copolymer base polymer (BP) and a carbon-carbon double bond (activation energy line-reactive compound) can be obtained by an addition reaction.
  • active energy ray-reactive compounds include compounds having an isocyanate group and a carbon-carbon double bond, compounds having a carboxyl group and a carbon-carbon double bond, glycidyl groups and a carbon-carbon double bond. and compounds having an amino group and a carbon-carbon double bond. These radiation reactive compounds may be used singly or in combination.
  • addition reaction examples include, for example: (1) using a hydroxyl group-containing monomer as a functional group-containing monomer component of the binary or higher (meth)acrylic acid ester copolymer base polymer (BP); (2) a carboxyl group as a functional group-containing monomer component of the base polymer (BP); (3) a method of subjecting the carboxyl group to an addition reaction with a glycidyl group of a compound having a glycidyl group and a carbon-carbon double bond (active energy ray-reactive compound) using a contained monomer; A method of using a glycidyl group-containing monomer as a group-containing monomer component and subjecting the glycidyl group to an addition reaction with a carboxyl group of a compound having a carbocisyl group and a carbon-carbon double bond (active energy ray-reactive compound); A method of using an amino group-containing monomer as a functional group-containing monomer component of the polymer (BP), and
  • the above binary or more (meth)acrylic acid ester copolymer base polymer (BP) containing functional groups The most preferred method is to use a hydroxy group-containing monomer as the monomer component and subject the hydroxy group to an addition reaction with an isocyanate group of a compound having an isocyanate group and a carbon-carbon double bond (active energy ray-reactive compound).
  • a compound having an isocyanate group and a carbon-carbon double bond includes, for example, an isocyanate compound having a (meth)acryloyloxy group.
  • 2-methacryloyloxyethyl isocyanate 4-methacryloyloxy-n-butyl isocyanate, 2-acryloyloxyethyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate and the like.
  • 2-methacryloyloxyethyl isocyanate is preferred from the viewpoint of versatility.
  • a polymerization inhibitor so that the active energy ray reactivity of the carbon-carbon double bond is maintained.
  • a quinone-based polymerization inhibitor such as hydroquinone monomethyl ether is preferable.
  • the amount of the polymerization inhibitor is not particularly limited, it is usually 0.01 parts by mass or more and 0.1 parts by mass with respect to 100 parts by mass of the (meth)acrylic acid ester copolymer base polymer (BP) of two or more elements. The following ranges are preferred.
  • the functional group of the (meth)acrylic acid ester copolymer (A2) is crosslinked by a crosslinking agent added later as a reaction point to further increase the molecular weight
  • a crosslinking agent added later as a reaction point to further increase the molecular weight
  • the cross-linking reaction It is preferred that the functional groups remain in the subsequent pressure-sensitive adhesive composition.
  • the isocyanate compound having the (meth)acryloyloxy group is 22 per mole of the total amount of hydroxy group-containing monomer component, which is the copolymer monomer component of the base polymer (BP). It is preferable to carry out the addition reaction using an amount in the range of mol % or more and 99 mol % or less. It is more preferably in the range of 40 mol % or more and 90 mol % or less, and still more preferably in the range of 50 mol % or more and 85 mol % or less.
  • (A2) is the n-butyl acrylate (n-BA) monomer, the functional group-containing monomer, and, if necessary, one or more monomers selected from the above-described monomers other than both of these monomers,
  • a mixture containing a predetermined amount as a copolymer monomer component is subjected to polymerization to synthesize a base polymer (BP), and then an active energy ray-reactive compound is subjected to an addition reaction in the presence of an organometallic catalyst.
  • the weight-average molecular weight (Mw) of the (meth)acrylic acid ester copolymer base polymer (A2) is preferably 100,000 or more from the viewpoint of improving the cohesive strength of the active energy ray-curable pressure-sensitive adhesive layer 3. It is preferably 1,500,000 or less from the viewpoint of application suitability of the solution of the adhesive composition of the active energy ray-curable adhesive layer 3 . That is, the weight average molecular weight (Mw) is preferably in the range of 100,000 to 1,500,000, more preferably in the range of 300,000 to 1,000,000.
  • the weight average molecular weight (Mw) is the weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography (GPC).
  • the acid value of the (meth)acrylic acid ester copolymer (A2) is not particularly limited as long as it does not interfere with the effects of the present invention, and may be 0 mgKOH/g. 2 and the active energy ray-curable adhesive layer 3, and from the viewpoint of improving the adhesive strength of the work processing adhesive tape 10 to the work before active energy ray irradiation, it is preferably 1.2 mgKOH/g or more. , it is preferably 17.8 mgKOH/g or less from the viewpoint of reducing the adhesive force of the adhesive tape 10 for work processing after irradiating the work with the active energy ray. That is, the acid value is preferably in the range of 1.2 mgKOH/g or more and 17.8 mgKOH/g or less.
  • the hydroxyl value of the (meth)acrylic acid ester copolymer (A2) is not particularly limited as long as it does not interfere with the effects of the present invention, but the above-mentioned intermediate layer 2 and the active energy ray-curable adhesive 10.2 mgKOH/g or more from the viewpoint of adhesion with the agent layer 3, improvement of the cohesive force of the adhesive layer 3, and control of the adhesive force of the adhesive tape 10 for work processing to the work before and after irradiation with active energy rays.79. It is preferably in the range of 2 mgKOH/g or less.
  • the carbon-carbon double bond concentration of the (meth)acrylic ester copolymer (A2) may be the concentration at which a sufficient effect of reducing the adhesive strength in the adhesive layer 3 after irradiation with active energy rays is obtained, and it is not unique depending on the usage conditions such as the irradiation amount of the active energy rays, but the carbon- The carbon double bond concentration is preferably in the range of 0.59 meq/g or more and 1.60 meq/g or less, and from the viewpoint of the balance between the effect and economy, 0.59 meq/g or more and 1.49 meq/g The following range is more preferable, and the range of 0.59 meq/g or more and 1.29 meq/g or less is particularly preferable.
  • the carbon-carbon double bond concentration is less than 0.59 meq/g, the effect of reducing the adhesive force in the adhesive layer 3 after irradiation with active energy rays is reduced, so that the workpiece processed from the adhesive tape 10 for workpiece processing is processed.
  • peeling off it becomes difficult to peel off, and there is a risk that troubles such as breakage of the processed work will increase.
  • the carbon-carbon double bond concentration exceeds 1.60 meq/g, the effect gradually saturates, which is not preferable from an economical point of view.
  • the copolymerization composition of the (meth)acrylic acid ester copolymer (A2) it is likely to gel during the addition reaction, and synthesis may be difficult.
  • Adhesion to the layer 3 may become insufficient.
  • Carbon-carbon double bond concentrations can be calculated.
  • the pressure-sensitive adhesive composition constituting the active energy ray-curable pressure-sensitive adhesive layer 3 of the present embodiment improves the cohesive force of the pressure-sensitive adhesive layer 3 by increasing the molecular weight of the (meth)acrylic acid ester copolymer (A2).
  • the (meth)acrylic acid ester copolymer (A2) In order to allow the (meth)acrylic acid ester copolymer (A2) to contain a functional group and a reactive cross-linking agent.
  • a cross-linking agent is not particularly limited, and the functional group possessed by the (meth)acrylic acid ester copolymer (A2), that is, typically a hydroxy group, or a carboxyl group introduced as necessary
  • a known cross-linking agent having a functional group capable of reacting with such as can be used.
  • polyisocyanate-based cross-linking agents for example, polyisocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, aziridine-based cross-linking agents, melamine resin-based cross-linking agents, urea resin-based cross-linking agents, acid anhydride compound-based cross-linking agents, and polyamine-based cross-linking agents
  • Cross-linking agents, carboxyl group-containing polymer-based cross-linking agents, and the like can be mentioned.
  • a polyisocyanate-based cross-linking agent an epoxy-based cross-linking agent or a metal chelate-based cross-linking agent, and it is more preferable to use a polyisocyanate-based cross-linking agent.
  • These cross-linking agents may be used alone or in combination of two or more.
  • the amount of the cross-linking agent is preferably in the range of 0.01 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the solid content of the (meth)acrylate copolymer (A2). It is more preferably in the range of 0.1 to 5.0 parts by mass, and particularly preferably in the range of 0.2 to 1.0 parts by mass.
  • Examples of the above-mentioned polyisocyanate-based cross-linking agent and epoxy-based cross-linking agent include those exemplified above as the cross-linking agent for the intermediate layer 2 .
  • the metal-based chelate cross-linking agent those capable of cross-linking hydroxyl groups are preferable, and specific examples thereof include titanium chelate compounds having Ti as the central metal and zirconium chelate compounds having Zr as the central metal. .
  • polyisocyanate compounds having an isocyanurate ring polyisocyanate compounds having an isocyanurate ring
  • adduct polyisocyanate compounds obtained by reacting trimethylolpropane and hexamethylene diisocyanate adduct polyisocyanate compounds obtained by reacting trimethylolpropane and tolylene diisocyanate, etc.
  • a polyisocyanate-based cross-linking agent can be preferably used.
  • a copolymer of n-butyl acrylate (n-BA) and 2-hydroxyethyl acrylate (2-HEA) as the base polymer of the (meth)acrylate copolymer (A2) When using a binary (meth)acrylic acid ester copolymer containing as a monomer component and using the above polyisocyanate-based cross-linking agent as a cross-linking agent, in the entire pressure-sensitive adhesive composition excluding the photopolymerization initiator described later, the The isocyanate group (NCO) possessed by the polyisocyanate cross-linking agent and the hydroxyl group (OH) possessed by the (meth)acrylic acid ester copolymer (A2) having a photosensitive carbon-carbon double bond introduced into the side chain.
  • NCO isocyanate group
  • OH hydroxyl group
  • the equivalent ratio (NCO/OH) is not particularly limited as long as it does not interfere with the effects of the present invention, but the cohesive force of the pressure-sensitive adhesive layer 3, the adhesion between the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3 , from the viewpoint of control of adhesive strength, etc., it is preferably in the range of 0.005 or more and 0.338 or less. Further, from the same point of view, the residual hydroxyl group concentration in the entire pressure-sensitive adhesive composition (excluding the photopolymerization initiator) after the cross-linking reaction by the polyisocyanate-based cross-linking agent is 0.04 mmol/g or more and 1.62 mmol/g or less. range, and more preferably, the carbon-carbon double bond concentration is in the range of 0.58 meq/g or more and 1.48 meq/g or less.
  • the adhesive composition forming the active energy ray-curable adhesive layer 3 of the present embodiment contains a photopolymerization initiator that generates radicals upon exposure to active energy rays.
  • the photopolymerization initiator receives irradiation of active energy rays with respect to the pressure-sensitive adhesive composition constituting the active energy ray-curable pressure-sensitive adhesive layer 3, generates radicals, and forms a (meth)acrylic acid ester copolymer (A2). initiates the cross-linking reaction of the photosensitive carbon-carbon double bonds introduced into the side chains of the .
  • the photopolymerization initiator is not particularly limited, and conventionally known ones can be used. Examples thereof include alkylphenone-based radical polymerization initiators, acylphosphine oxide-based radical polymerization initiators, oxime ester-based radical polymerization initiators, and the like. Examples of the alkylphenone-based radical polymerization initiator include benzylmethylketal-based radical polymerization initiators, ⁇ -hydroxyalkylphenone-based radical polymerization initiators, aminoalkylphenone-based radical polymerization initiators, and the like.
  • benzyl methyl ketal-based radical polymerization initiator examples include, for example, 2,2'-dimethoxy-1,2-diphenylethan-1-one (for example, trade name: Omnirad 651, IGM Resins B.V. made) and the like.
  • ⁇ -hydroxyalkylphenone-based radical polymerization initiator examples include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.
  • aminoalkylphenone-based radical polymerization initiators include, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins B.V. V.) or 2-benzylmethyl 2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (trade name: Omnirad 369, manufactured by IGM Resins B.V.).
  • acylphosphine oxide-based radical polymerization initiators include, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: OmniradTPO, manufactured by IGM Resins B.V.), bis( 2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: Omnirad819, manufactured by IGM Resins B.V.), and oxime ester-based radical polymerization initiators include (2E)-2-(benzoyloxyimino )-1-[4-(phenylthio)phenyl]octan-1-one (trade name: OmniradOXE-01, manufactured by IGM Resins B.V.) and the like. These photopolymerization initiators may be used alone or in combination of two or more.
  • the amount of the photopolymerization initiator added is based on 100 parts by mass of the solid content of the (meth)acrylic acid ester copolymer (A2) in which a photosensitive carbon-carbon double bond is introduced in the side chain. , 0.1 parts by mass or more and 10.0 parts by mass or less.
  • the amount of the photopolymerization initiator added is less than 0.1 part by mass, the photoreactivity with respect to active energy rays is insufficient, so even if the active energy rays are irradiated, the (meth)acrylic acid ester copolymer ( The photo-radical cross-linking reaction of A2) does not occur sufficiently, and as a result, the effect of reducing the adhesive force in the adhesive layer 3 after irradiation with active energy rays is reduced, and when peeling the processed work from the work processing adhesive tape 10 In addition, peeling becomes difficult, and problems such as breakage of the machined work may increase.
  • the amount of the photopolymerization initiator added exceeds 10.0 parts by mass, the effect is saturated, which is not preferable from the viewpoint of economy.
  • the pressure-sensitive adhesive layer 3 may turn yellow, resulting in poor appearance.
  • compounds such as dimethylaminoethyl methacrylate and isoamyl 4-dimethylaminobenzoate may be added to the adhesive composition as sensitizers for such photopolymerization initiators.
  • the pressure-sensitive adhesive composition constituting the active energy ray-curable pressure-sensitive adhesive layer 3 of the present embodiment may optionally further contain a polyfunctional acrylic monomer, a polyfunctional acrylic oligomer, a Additives such as tackifiers, fillers, antioxidants, colorants, flame retardants, antistatic agents, surfactants, silane coupling agents and leveling agents may be added.
  • the thickness of the active energy ray-curable pressure-sensitive adhesive layer 3 is not particularly limited as long as it does not interfere with the effects of the present invention, and may be adjusted as appropriate according to the processing of the work. and the adhesive layer 3, and from the viewpoint of improving the adhesive strength of the work processing adhesive tape 10 to the work before the active energy ray irradiation and reducing the adhesive strength after the active energy ray irradiation, for example, it is 5 ⁇ m or more.
  • the thickness is preferably 150 ⁇ m or less from the viewpoints of coating/drying suitability of the solution of the pressure-sensitive adhesive composition of the pressure-sensitive adhesive layer 3 and economy. That is, the thickness of the adhesive layer 3 is preferably in the range of 5 ⁇ m to 150 ⁇ m, more preferably in the range of 8 ⁇ m to 50 ⁇ m.
  • a work processing pressure-sensitive adhesive tape 10 of the present embodiment has a structure including a substrate film 1 made of a polyester-based resin composition, an intermediate layer 2, and an active energy ray-curable pressure-sensitive adhesive layer 3 in this order.
  • a release liner is provided on the surface of the pressure-sensitive adhesive layer 3 opposite to the surface in contact with the intermediate layer 2 .
  • the release liner include, but are not particularly limited to, synthetic resins such as polyethylene, polypropylene, and polyethylene terephthalate, papers, and the like.
  • the surface of the release liner may be subjected to a release treatment with a silicone-based release agent, a long-chain alkyl-based release agent, a fluorine-based release agent, or the like, in order to enhance the release property from the adhesive layer 3 .
  • the thickness of the release liner is not particularly limited, but those in the range of 10 ⁇ m or more and 200 ⁇ m or less can be preferably used.
  • the method for manufacturing the work processing adhesive tape 10 is not particularly limited, it can be manufactured, for example, by the following method.
  • a substrate film 1 made of a polyester-based resin composition is prepared.
  • a solution of the resin composition for the intermediate layer 2, which is the material for forming the intermediate layer 2 is prepared.
  • a solution of the resin composition can be prepared, for example, by uniformly mixing and stirring the (meth)acrylic acid ester copolymer (A1), which is a component of the intermediate layer 2, the cross-linking agent, and the diluent solvent.
  • the solvent for example, general-purpose organic solvents such as toluene and ethyl acetate can be used.
  • the solution of the resin composition for the intermediate layer 2 is applied onto the base film 1 and dried to form the intermediate layer 2 having a predetermined thickness.
  • the coating method is not particularly limited, and for example, a die coater, a comma coater (registered trademark), a gravure coater, a roll coater, a reverse coater, or the like can be used.
  • the drying conditions are not particularly limited, it is preferable that the drying temperature is in the range of 80° C. or higher and 150° C. or lower, and the drying time is in the range of 0.5 minute or longer and 5 minutes or shorter.
  • the exposed surface of the intermediate layer 2 formed on the base film 1 is laminated with the release-treated surface side of the release liner.
  • a release liner is prepared, and a solution of an adhesive composition for the adhesive layer 3, which is a material for forming the adhesive layer 3, is prepared.
  • the solution of the adhesive composition is prepared, for example, by uniformly mixing and stirring the (meth)acrylic acid ester copolymer (A2), which is a component of the adhesive layer 3, the cross-linking agent, the photopolymerization initiator, and the diluent solvent. can be made.
  • the solvent for example, general-purpose organic solvents such as toluene and ethyl acetate can be used.
  • the solution of the adhesive composition is applied to the release-treated surface side of the release liner and dried to form an adhesive layer 3 having a predetermined thickness. do.
  • the coating method is not particularly limited, and the same method as for the intermediate layer 2 can be used.
  • the drying conditions are not particularly limited, and the same conditions as those for the intermediate layer 2 can be used.
  • the exposed surface of the adhesive layer 3 formed on the release-treated surface side of the release liner is laminated with the surface from which the release liner of the intermediate layer 2 formed on the previously prepared base film 1 has been peeled off. to form a laminate.
  • the laminate is aged, for example, in an environment of 40° C. for 72 hours to allow the (meth)acrylic acid ester copolymer of the intermediate layer 2 and the pressure-sensitive adhesive layer 3 to react with the cross-linking agent, thereby cross-linking and Harden.
  • the pressure-sensitive adhesive tape 10 for work processing is provided with an intermediate layer 2, an active energy ray-curable pressure-sensitive adhesive layer 3, and a release liner in order from the base film side on a base film 1 made of a polyester-based resin composition. can be manufactured.
  • the intermediate layer 2 and the pressure-sensitive adhesive layer 3 may be bonded together to form a laminate.
  • a laminate having a release liner on the adhesive layer 3 is also treated as the adhesive tape 10 for work processing.
  • Another method for manufacturing the work processing adhesive tape 10 includes, for example, the following method. First, a substrate film 1 made of a polyester-based resin composition is prepared. Next, a solution of the resin composition for the intermediate layer 2 and a solution of the adhesive composition for the adhesive layer 3 are prepared. Next, using a die coater having two ejection ports, the intermediate layer 2 and the adhesive layer 3 are coated on the base film 1 in this order from the base film side by a wet-on-wet coating method. , the respective solutions are simultaneously extrusion-coated and dried to form the intermediate layer 2 and the pressure-sensitive adhesive layer 3 having a predetermined thickness. Then, the exposed surface of the pressure-sensitive adhesive layer 3 is laminated with the release-treated surface side of the release liner to form a laminate.
  • the laminate is aged, for example, in an environment of 40° C. for 72 hours to crosslink and cure by reacting the (meth)acrylic acid ester copolymer of the intermediate layer 2 and the pressure-sensitive adhesive layer 3 with the crosslinking agent.
  • the pressure-sensitive adhesive tape 10 for work processing is provided with an intermediate layer 2, an active energy ray-curable pressure-sensitive adhesive layer 3, and a release liner in order from the base film side on a base film 1 made of a polyester-based resin composition. can be manufactured.
  • the total thickness of the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3 is not particularly limited as long as the effects of the present invention are not hindered.
  • the thickness may be appropriately adjusted depending on the processing, but for example, it is preferably in the range of 10 ⁇ m or more and 300 ⁇ m or less, more preferably in the range of 13 ⁇ m or more and 150 ⁇ m or less. More specifically, for example, when dicing a fragile work such as the glass substrate 30 or a hard work such as a sapphire glass substrate, the total thickness is preferably in the range of 13 ⁇ m to 40 ⁇ m. Further, for example, when grinding a semiconductor wafer having a circuit formed on its surface, the total thickness is preferably in the range of 20 ⁇ m or more and 135 ⁇ m or less.
  • the work processing adhesive tape 10 needs to have an initial adhesive force high enough to firmly hold and fix the work on the active energy ray-curable adhesive layer 3 so that it does not move during work processing.
  • the active energy ray-curable adhesive layer 3 is cured and shrunk by irradiation with an active energy ray so that the processed work can be easily separated from the work processing adhesive tape 10. It is necessary to reduce the adhesive strength significantly.
  • Examples of the active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, ⁇ rays, and ⁇ rays.
  • ultraviolet rays (UV) and electron beams (EB) are preferred, and ultraviolet rays (UV) are particularly preferred.
  • the light source for irradiating the ultraviolet rays (UV) is not particularly limited, but for example, black light, ultraviolet fluorescent lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon. A lamp or the like can be used.
  • UV ultraviolet
  • the irradiation light amount of the ultraviolet (UV) is not particularly limited, and for example, it is preferably in the range of 100 mJ/cm 2 or more and 2,000 mJ/cm 2 or less, and 300 mJ/cm 2 or more and 1,000 mJ/cm 2 or less. A range is more preferred.
  • the adhesive strength (initial adhesive strength) of the work processing adhesive tape 10 to a glass plate before ultraviolet irradiation is preferably in the range of 5.0 N/25 mm or more and 26.0 N/25 mm or less, and 19.0 N/25 mm or more. A range of 25.0 N/25 mm or less is more preferable. If the adhesive strength to the glass plate before ultraviolet irradiation is less than 5.0 N/25 mm, for example, when dicing the glass substrate 30, the glass substrate 30 is placed on the adhesive layer 3 of the adhesive tape 10 for work processing. Since it is difficult to hold and fix the glass chips 30a firmly, it may not be possible to sufficiently suppress the scattering and displacement of the glass chips 30a, and the chipping of the glass chips 30a caused by the displacement.
  • the glass chip 30a is excessively held on the adhesive layer 3, so the work processing adhesive tape 10 after ultraviolet irradiation There is a possibility that the glass chip 30a cannot be picked up satisfactorily because the adhesive strength of the glass chip 30a is not sufficiently reduced.
  • the adhesive strength of the work processing adhesive tape 10 to a glass plate after ultraviolet irradiation is preferably in the range of 0.01 N/25 mm or more and 0.5 N/25 mm or less, and 0.02 N/25 mm or more and 0.25 N. /25 mm or less is more preferable.
  • the adhesive strength of the work processing adhesive tape 10 to the glass plate after ultraviolet irradiation is less than 0.01 N/25 mm, for example, after dicing the glass substrate 30, the glass chip 30a is picked up from the work processing adhesive tape 10. During the process, the glass chip 30a may be unintentionally peeled off or deviated from the work processing adhesive tape 10, and thus may not be picked up properly.
  • the adhesive strength after ultraviolet irradiation to the glass plate exceeds 0.5 N/25 mm, for example, when the glass chips 30a are individually picked up, the adhesive strength is not sufficiently reduced, and the glass chips 30a are damaged. There is a possibility that it may not be picked up well. Moreover, even if it can be picked up, there is a possibility that adhesive residue may occur.
  • the adhesive strength in the present invention is the adhesive strength (N/25 mm) measured by the 180° peeling method according to JIS Z0237:2009, and the details of the measuring method are as described in the test method described later.
  • the adhesive strength after ultraviolet irradiation is such that the integrated amount of light is 300 mJ/cm 2 at an irradiation intensity of 75 mW/cm 2 from the base film 1 side of the work processing adhesive tape 10 using a high-pressure mercury lamp as a light source. was measured after irradiating with ultraviolet rays (UV) having a center wavelength of 365 nm.
  • the adhesive strength (initial adhesive strength) of the work processing adhesive tape 10 to a stainless steel plate (SUS304BA plate) before ultraviolet irradiation is preferably in the range of 5.0 N / 25 mm or more and 26.0 N / 25 mm or less, More preferably, the range is 19.0 N/25 mm or more and 25.0 N/25 mm or less. If the adhesive strength to the stainless steel plate (SUS304BA plate) before ultraviolet irradiation is less than 5.0 N/25 mm, for example, when dicing the glass substrate 30, it cannot withstand the load and water pressure of the dicing blade 40 and washing water.
  • the work processing adhesive tape 10 may be peeled off from the ring frame 20 made of SUS or slipped. Further, for example, when grinding the semiconductor wafer 50 , grinding water may enter the interface between the semiconductor wafer 50 and the adhesive layer 3 .
  • the adhesive force to the stainless steel plate (SUS304BA plate) before ultraviolet irradiation exceeds 25.0 N/25 mm, for example, in the work dicing process, the SUS ring frame 20 is excessively attached on the adhesive layer 3. Since it is held and fixed, there is a risk that the adhesive layer 3 will be transferred to the ring frame made of SUS when peeling off the unnecessary workpiece processing adhesive tape 10 from the ring frame after the required steps.
  • the semiconductor wafer 50 is held and fixed on the adhesive layer 3 excessively strongly, so that the adhesive strength of the work processing adhesive tape 10 after irradiation with ultraviolet rays is not sufficiently reduced.
  • the adhesive layer 3 may be transferred or left behind on the surface of the thinned semiconductor wafer 50'.
  • the adhesive strength of the work processing adhesive tape 10 to a stainless steel plate (SUS304BA plate) after ultraviolet irradiation is preferably in the range of 0.01 N/25 mm or more and 0.5 N/25 mm or less, and 0.02 N/ More preferably, it is in the range of 25 mm or more and 0.25 N/25 mm or less.
  • the adhesive strength of the work processing adhesive tape 10 to a stainless steel plate (SUS304BA plate) after ultraviolet irradiation is within the above range, for example, after grinding the semiconductor wafer 50, the work processing adhesive tape 10 is thinned into a semiconductor wafer.
  • Adhesive for work processing without transferring the adhesive layer 3 to the surface of the thinned semiconductor wafer 50' or leaving adhesive residue on the surface of the thinned semiconductor wafer 50' when peeling from the wafer 50', and without damaging the thinned wafer 50'.
  • the tape 10 can be easily peeled off.
  • the base film 1 made of a polyester-based resin composition and the active energy ray-curable pressure-sensitive adhesive layer 3 are bonded together before and after the irradiation of the active energy ray.
  • the adhesive since the adhesive is well adhered via the intermediate layer 2, for example, even when used as a backgrinding tape for ultra-thin semiconductor wafers, it is active at the time of peeling.
  • the energy ray-curable pressure-sensitive adhesive layer can be peeled off from the semiconductor wafer without being transferred, and is used as a dicing tape for cutting a fragile work such as a glass substrate or a hard work such as a sapphire glass substrate.
  • the work processing pressure-sensitive adhesive tape 10 of the present embodiment can be suitably used for processing and transporting works such as ceramics and electronic device members as well as semiconductor wafers and optical members.
  • TDI-based polyisocyanate-based cross-linking agent manufactured by Tosoh Corporation (trade name: Coronate L-45E, solid content concentration: 45% by mass, isocyanate group content in solution: 8.05% by mass, Isocyanate group content in solid content: 17.89% by mass, calculated number of isocyanate groups: average 2.8 per molecule, molecular weight: 656.64).
  • the glass transition temperature (Tg), weight average molecular weight (Mw), solid content acid value, and solid content hydroxyl value of the synthesized (meth)acrylic acid ester copolymers (A1-b') to (A1-s') are They were as shown in Tables 1-4 and 9, respectively.
  • n-BA n-butyl acrylate
  • Photosensitive carbon-carbon double bond is introduced into the side chain of the (meth)acrylic ester copolymer base polymer (BP) as the main component (meth)acrylic ester copolymer (A2-a' ) to (A2-j′) were synthesized.
  • a copolymer monomer component for synthesizing a (meth)acrylic acid ester copolymer base polymer (BP) having n-butyl acrylate (n-BA) as the main component of the copolymer monomer - Methyl methacrylate (MMA, molecular weight: 100.12, homopolymer Tg: 105°C); - n-butyl acrylate (n-BA, molecular weight: 128.17, homopolymer Tg: -54°C); - 2-ethylhexyl acrylate (2-EHA, molecular weight: 184.3, Tg: -70°C); - 2-hydroxyethyl acrylate (2-HEA, molecular weight: 116.12, Tg: -15 ° C.); ⁇ Methacrylic acid (MAA, molecular weight: 86.06: Tg: 228°C) prepared.
  • MMA Methyl methacrylate
  • TDI-based polyisocyanate-based cross-linking agent manufactured by Tosoh Corporation (trade name: Coronate L-45E, solid content concentration: 45% by mass, isocyanate group content in solution: 8.05% by mass, Isocyanate group content in solid content: 17.89% by mass, calculated number of isocyanate groups: average 2.8 per molecule, molecular weight: 656.64).
  • n-BA n-butyl acrylate
  • 2-HEA 2-hydroxyethyl acrylate
  • MAA methacrylic acid
  • acylphosphine oxide-based photopolymerization initiator (trade name: Omnirad 819) manufactured by Tosoh Corporation as a cross-linking agent, and a TDI-based polyisocyanate-based cross-linking agent manufactured by Tosoh Corporation (trade name: Coronate L-45E, Solid content concentration: 45% by mass) was blended at a ratio of 0.45 parts by mass (0.20 parts by mass in terms of solid content, 0.30 mmol), diluted with ethyl acetate and stirred to obtain a solid content concentration of 30% by mass.
  • a solution of the adhesive composition (A2-a) for the adhesive layer 3 was prepared.
  • the isocyanate group (NCO) and the side chain of the polyisocyanate-based cross-linking agent have a photosensitive carbon-carbon double bond.
  • the equivalent ratio (NCO/OH) to the hydroxyl group (OH) of the (meth)acrylic acid ester copolymer (A2-a′) is 0.007, the residual hydroxyl group concentration is 0.99 mmol/g, and the carbon-carbon double The binding content was 0.58 mmol/g.
  • 2-isocyanatoethyl methacrylate (trade name: Karenz MOI), which is an active energy ray-reactive compound, is added to these (meth)acrylate copolymer base polymers (BP-b) to (BP-j).
  • the addition reaction was carried out with the amounts shown in Tables 4 to 6, respectively, and in the same manner as above, a photosensitive carbon-carbon double bond was introduced into the side chain (meth) acrylic acid ester co- Solutions of polymers (A2-b') to (A2-j') were synthesized respectively.
  • the glass transition temperature (Tg) of the synthesized (meth) acrylic ester copolymer base polymer (BP-b) ⁇ (BP-j), and the (meth) acrylic ester copolymer (A2-b') ⁇ (The weight average molecular weight (Mw), solid content hydroxyl value, solid content acid value, and carbon-carbon double bond concentration in A2-j') were as shown in Tables 4 to 6, respectively.
  • the isocyanate group (NCO) and the side chain of the polyisocyanate-based cross-linking agent have a photosensitive carbon-carbon double Equivalent ratio (NCO/OH) with hydroxyl groups (OH) of (meth)acrylic acid ester copolymers (A2-b) to (A2-j) having side chains introduced with bonds (NCO/OH), residual hydroxyl group concentration, and carbon -
  • the carbon double bond concentration was as follows.
  • Example 1 As the base film 1, a polyethylene terephthalate (PET) film (trade name: Emblet #100, thickness: 100 ⁇ m) manufactured by Unitika Ltd. is used, and the thickness of the intermediate layer 2 after drying is 10 ⁇ m. Thus, the solution of the intermediate layer resin composition (A1-a) was applied and heated at a temperature of 100° C. for 3 minutes to dry the solvent, thereby forming an intermediate layer 2 on the base film 1. .
  • PET polyethylene terephthalate
  • the active energy ray-curable adhesive layer 3 after drying is applied to the release-treated surface side of a release liner (trade name: NS-38+A, material: polyethylene terephthalate, thickness: 38 ⁇ m) manufactured by Nakamoto Pax Co., Ltd.
  • a release liner (trade name: NS-38+A, material: polyethylene terephthalate, thickness: 38 ⁇ m) manufactured by Nakamoto Pax Co., Ltd.
  • the active energy ray-curable adhesive The surface of the intermediate layer 2 formed on the substrate film 1 was laminated onto the layer 3 . Subsequently, it was stored at a temperature of 40° C. for 72 hours to crosslink and cure the active energy ray-curable pressure-sensitive adhesive layer 3, thereby producing a work processing pressure-sensitive adhesive tape 10(a).
  • Examples 2 to 15 The solution of the resin composition (A1-a) for the intermediate layer 2 was changed to the solution of the resin composition (A1-b) to (A1-o) for the intermediate layer 2 as shown in Tables 1 to 4, respectively.
  • Work processing pressure-sensitive adhesive tapes 10(b) to 10(o) were produced in the same manner as in Example 1 except for the above.
  • Example 16-24 A solution of the adhesive composition (A2-a) for the active energy ray-curable adhesive layer 3 was added to the adhesive composition (A2-b) for the adhesive composition 3 as shown in Tables 4 to 6, respectively.
  • ⁇ (A2-j) in the same manner as in Example 2 except that the blending amount of the cross-linking agent in the adhesive composition was changed only in Examples 22 to 24.
  • p)-10(x) were produced.
  • Example 5 A work processing adhesive tape 10 (jj) was produced in the same manner as in Example 1 except that the intermediate layer 2 was not provided, as shown in Table 10.
  • a work processing pressure-sensitive adhesive tape 10 (kk) was produced in the same manner as in Example 1, except that the resin composition solution was used and the thickness of the intermediate layer 2 was changed to 2 ⁇ m, as shown in Table 10. did.
  • the release liner is peeled off from the adhesive tape 10 for work processing, the exposed surface of the adhesive layer 3 is placed on one surface of the adherend, and a 2 kg roller is applied 1 A load was applied by reciprocating the laminate, and the laminate was left for 20 minutes. The length of the bonded portion was 80 mm.
  • the work processing adhesive tape 10 was peeled from the adherend at a peeling speed of 300 mm / min and a peeling angle of 180° by a 180° peeling method according to JIS Z0237: 2009, The adhesive strength (unit: N/25mm) was measured. The number of samples for measurement was 3, and the average value of 3 measurements was taken as the adhesive strength before ultraviolet (UV) irradiation.
  • the work processing adhesive tape 10 prepared in Examples and Comparative Examples and the adherend were bonded together and allowed to stand for 20 minutes.
  • ultraviolet rays (UV) having a central wavelength of 365 nm were irradiated to cure the pressure-sensitive adhesive layer 3 .
  • the ultraviolet irradiation conditions were irradiation intensity: 75 mW/cm 2 and integrated light amount: 300 mJ/cm 2 .
  • the adhesive strength (unit: N/25 mm) was measured in the same manner as described above, and the average value of the three measurements was taken as the adhesive strength after ultraviolet (UV) irradiation.
  • the former (before ultraviolet irradiation) is the evaluation of adhesive residue on the surface of the ring frame 20 when the outer edge portion of the work processing adhesive tape 10 not irradiated with ultraviolet rays (UV) is peeled off from the ring frame 20 after the dicing process is completed. is assumed.
  • the latter (after ultraviolet irradiation) 9 is the amount of adhesive residue on the surface of the semiconductor wafer 50' when the adhesive tape 10 for work processing irradiated with ultraviolet light is peeled off from the thinned semiconductor wafer 50' after grinding the semiconductor wafer 50. It is a hypothetical evaluation.
  • the adhesive residue was evaluated according to the following criteria. An evaluation of ⁇ was judged to be practically acceptable. Evaluation criteria ⁇ : No adhesive residue ⁇ : Adhesive residue
  • Film base adhesive tape (trade name: No. 626050 film tape manufactured by Maxell; 180° peeling adhesive strength to SUS304BA plate: 10.8 N/25 mm) was pasted on the formed lattice and peeled off by hand.
  • the adhesiveness between the intermediate layer 2 and the active energy ray-curable pressure-sensitive adhesive layer 3 was evaluated by counting the number of squares from which the pressure-sensitive adhesive layer 3 was peeled off.
  • the adhesion between the base film 1 and the active energy ray-curable pressure-sensitive adhesive layer 3 is evaluated.
  • the adhesive residue on the surface of the semiconductor wafer 50' when the adhesive tape 10 for work processing irradiated with ultraviolet rays is peeled off from the thinned semiconductor wafer 50' at high speed is assumed. It is what I did. That is, if the adhesiveness is good, even if the work processing adhesive tape 10 irradiated with ultraviolet rays is peeled off at a high speed, no adhesive remains on the surface of the thinned semiconductor wafer 50'.
  • the intermediate layer 2 and the active energy ray-curable Adhesion with the pressure-sensitive adhesive layer 3 was evaluated. This evaluation is based on, for example, when the outer edge portion of the work processing adhesive tape 10 not irradiated with ultraviolet rays (UV) is peeled off from the ring frame 20 at high speed after the dicing process is completed, the work processing adhesive tape 10 attached to the ring frame 20 is used.
  • UV ultraviolet rays
  • ⁇ ⁇ The number of squares where the adhesive layer has peeled off for 100 squares is in the range of 0 (0/100)
  • ⁇ ⁇ The number of squares where the adhesive layer has peeled off for 100 squares is 1 to 100 (1/100- 100/100) range
  • Evaluation Results Tables 11 to 20 show the physical property evaluation results of the work processing adhesive tapes 10(a) to 10(kk) produced in Examples 1 to 31 and Comparative Examples 1 to 6 above.
  • the adhesive tapes for work processing 10(a) to 10(ee) of Examples 1 to 31 satisfying the requirements of the present invention were used as a base for the purpose of improving the work processing quality. Even when a film made of a polyester resin composition is used as the material film, the adhesive strength before and after ultraviolet irradiation, the adhesive residue on the adherend, and the adhesion of the active energy ray-curable adhesive layer It was confirmed that favorable results were obtained in both evaluations. That is, when the adhesive tape for work processing of the present invention is used as a backgrinding tape for ultrathinning of a semiconductor wafer, it is possible to uniformly ultrathinize the semiconductor wafer by grinding.
  • the active energy ray-curable pressure-sensitive adhesive layer can be peeled off without being transferred to the ultra-thin semiconductor wafer.
  • the dicing tape holding the workpieces will not peel off from the ring frame during the dicing process.
  • the pick-up property of the chips after dicing was also good, and when the dicing tape was peeled off from the ring frame after completion of pick-up, it was judged that the tape could be peeled off without leaving adhesive residue on the ring frame.
  • the pressure-sensitive adhesive tape for work processing 10 (ff) of Comparative Example 1 and the pressure-sensitive adhesive tape for work processing 10 (gg) of Comparative Example 2 are made of a ternary (meth)acrylic acid ester copolymer for the intermediate layer 2. Since the content of methyl acrylate, which is the copolymer monomer component of (A1), exceeds the upper limit of the claimed range, in the evaluation of adhesive residue before UV irradiation, adhesive residue on the surface of the stainless steel plate (SUS304BA plate) was observed.
  • the pressure-sensitive adhesive tape for work processing 10 (hh) of Comparative Example 3 and the pressure-sensitive adhesive tape for work processing 10 (ii) of Comparative Example 4 use the ternary (meth)acrylic acid ester copolymer (A1) of the intermediate layer 2 Since the content of methacrylic acid, which is a copolymer monomer component, is below the lower limit of the scope of claims, in the evaluation of adhesion by a cross-cut test before ultraviolet irradiation, the workpieces of Examples 2, 4, 6 and 7 Compared with adhesive tapes 10(b), 10(d), 10(f) and 10(g) for processing, much peeling of the adhesive layer was confirmed. Also, in the evaluation of adhesive residue before UV irradiation, adhesive residue was observed on the surface of the stainless steel plate (SUS304BA plate).
  • the work processing pressure-sensitive adhesive tape 10 (jj) of Comparative Example 5 does not include the intermediate layer 2, in the adhesion evaluation by the cross-cut test before ultraviolet irradiation, the pressure-sensitive adhesive layer was completely peeled (100/100 ) was observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

La présente invention concerne un ruban adhésif pour le traitement d'une pièce à usiner, le ruban adhésif pouvant être utilisé même en tant que ruban de meulage arrière qui peut subir le meulage ou la réduction de l'épaisseur d'une tranche de semi-conducteur et pouvant également être utilisé même en tant que ruban de découpage en dés qui peut subir la coupe d'une pièce à usiner fragile telle qu'un substrat en verre. Plus spécifiquement, le ruban adhésif pour le traitement d'une pièce à usiner selon la présente invention comprend un film de matériau de base composé d'une composition de résine à base de polyester, une couche intermédiaire et une couche d'agent adhésif durcissable par rayonnement d'énergie active dans l'ordre indiqué, la couche intermédiaire étant composée d'une composition de résine qui contient un copolymère d'ester d'acide (méth)acrylique ternaire ou supérieur (A1) incluant de l'acrylate de méthyle et de l'acide méthacrylique en tant que composants monomères de copolymère, la couche intermédiaire incluant en outre 47 à 67 parties en masse de l'acrylate de méthyle et dans une plage de 2 à 7 parties en masse de l'acide méthacrylique, la quantité totale de composants monomères de copolymère constituant le copolymère acrylique (A1) étant de 100 parties en masse en tant que référence et la couche d'agent adhésif durcissable par rayonnement d'énergie active étant composée d'une composition d'agent adhésif composée d'une composition d'agent adhésif qui contient un agent de réticulation et un copolymère d'ester d'acide (méth)acrylique (A2) obtenu par l'introduction d'une double liaison carbone-carbone photosensible dans une chaîne latérale d'un polymère de base de copolymère d'ester d'acide (méth)acrylique ayant de l'acrylate de n-butyle en tant que composant principal de monomères de copolymère.
PCT/JP2022/001414 2021-03-31 2022-01-17 Ruban adhésif pour le traitement d'une pièce à usiner Ceased WO2022209152A1 (fr)

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JP2010232301A (ja) * 2009-03-26 2010-10-14 Sekisui Chem Co Ltd ダイシングテープ及び半導体チップの製造方法
JP2014200949A (ja) * 2013-04-02 2014-10-27 三井化学東セロ株式会社 拡張性フィルム、それを用いた半導体装置の製造方法
JP2015056446A (ja) * 2013-09-10 2015-03-23 古河電気工業株式会社 半導体ウエハ表面保護用粘着テープおよび半導体ウエハの加工方法
WO2020195744A1 (fr) * 2019-03-27 2020-10-01 リンテック株式会社 Feuille de traitement de pièce à travailler

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JP5770038B2 (ja) 2011-07-25 2015-08-26 リンテック株式会社 粘着シート
JP6839925B2 (ja) 2016-03-16 2021-03-10 リンテック株式会社 半導体加工用シート
JP2018115333A (ja) * 2018-03-20 2018-07-26 リンテック株式会社 粘着テープおよび半導体装置の製造方法
CN112400216B (zh) * 2018-06-26 2025-04-25 琳得科株式会社 半导体加工用粘着胶带及半导体装置的制造方法

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JP2008050406A (ja) * 2006-08-22 2008-03-06 Nitto Denko Corp 加工用粘着シート
JP2010232301A (ja) * 2009-03-26 2010-10-14 Sekisui Chem Co Ltd ダイシングテープ及び半導体チップの製造方法
JP2014200949A (ja) * 2013-04-02 2014-10-27 三井化学東セロ株式会社 拡張性フィルム、それを用いた半導体装置の製造方法
JP2015056446A (ja) * 2013-09-10 2015-03-23 古河電気工業株式会社 半導体ウエハ表面保護用粘着テープおよび半導体ウエハの加工方法
WO2020195744A1 (fr) * 2019-03-27 2020-10-01 リンテック株式会社 Feuille de traitement de pièce à travailler

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