WO2020110548A1 - Feuille de découpage en dés pour découpage en dés au plasma - Google Patents

Feuille de découpage en dés pour découpage en dés au plasma Download PDF

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Publication number
WO2020110548A1
WO2020110548A1 PCT/JP2019/042095 JP2019042095W WO2020110548A1 WO 2020110548 A1 WO2020110548 A1 WO 2020110548A1 JP 2019042095 W JP2019042095 W JP 2019042095W WO 2020110548 A1 WO2020110548 A1 WO 2020110548A1
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WIPO (PCT)
Prior art keywords
dicing
sensitive adhesive
pressure
mass
active energy
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PCT/JP2019/042095
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English (en)
Japanese (ja)
Inventor
由希 森田
孝斉 福元
卓生 西田
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リンテック株式会社
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Priority to JP2020520180A priority Critical patent/JP6719694B1/ja
Publication of WO2020110548A1 publication Critical patent/WO2020110548A1/fr

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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
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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]

Definitions

  • the present invention relates to a dicing sheet that can be suitably used for plasma dicing.
  • wafers such as silicon and gallium arsenide, and various packages (hereinafter, these may be collectively referred to as “workpieces”) are manufactured in a large diameter state, and these are small element pieces (hereinafter, “chips”). It may be described as ".”), and is individually separated (picked up) and then transferred to a mounting step which is the next step.
  • the work is attached to a dicing sheet including a base material and an adhesive layer, a predetermined position on the work is cut on the dicing sheet, and individual chips are cut and separated.
  • a rotating blade or a laser beam has hitherto been often used, but in recent years, cutting using plasma has also been performed.
  • the dicing width can be made narrower, the processing time can be shortened because dicing can be performed at once, and cutting pieces are less likely to occur, Since it is hard to give a shock to the work, there is an advantage that damage to the work or the chip can be suppressed.
  • Patent Document 1 discloses an example of a plasma dicing method.
  • Patent Document 1 discloses a method of performing plasma dicing while holding a work by electrostatic attraction.
  • Patent Document 2 discloses a dicing sheet for use in plasma dicing.
  • plasma dicing unlike blade dicing or laser dicing using laser light, it is necessary to place a laminate of a work and a dicing sheet under vacuum conditions (low pressure conditions) in order to generate plasma. Due to this, in the plasma dicing, the dicing sheet may be peeled off from the supporting base holding the dicing sheet, and as a result, proper dicing may not be performed.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a dicing sheet for plasma dicing that can suppress peeling of the dicing sheet from the support during plasma dicing. ..
  • the present invention is a dicing sheet for plasma dicing, comprising a substrate and an adhesive layer laminated on one side of the substrate, wherein the dicing sheet for plasma dicing is provided.
  • the surface resistivity measured from the said base material side surface in the said dicing sheet for plasma dicing is 1.0*10 ⁇ 15 >(ohm)/sq or more (invention 2).
  • the thickness of the base material is preferably 50 ⁇ m or more and 200 ⁇ m or less (Invention 3).
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m or more and 50 ⁇ m or less (Invention 4).
  • the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive having no active energy ray curability (Invention 5).
  • the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive having an active energy ray curability, and the pressure-sensitive adhesive has a functional group having a curable active energy ray in a side chain thereof. It is preferable to include an acrylic copolymer (Invention 6).
  • the plasma dicing dicing sheet according to the present invention can prevent the dicing sheet from peeling off from the support during plasma dicing.
  • the dicing sheet for plasma dicing according to the present embodiment (hereinafter, may be simply referred to as “dicing sheet”) includes a base material and an adhesive layer laminated on one side of the base material.
  • the mass reduction rate of the dicing sheet when the dicing sheet is left standing for 60 minutes in an environment of atmospheric pressure 0.1 MPa and temperature 25° C. Is 0.4% or less, preferably 0.39% or less, and particularly preferably 0.38% or less.
  • the lower limit of the mass reduction rate is preferably 0%, that is, no volatile component is released at all, but when it is difficult, for example, 0.01% or more. Good.
  • the details of the method for measuring the above-mentioned mass reduction rate are as described in the test examples described later.
  • the surface resistivity measured from the surface on the base material side is preferably 1.0 ⁇ 10 15 ⁇ /sq or more, and particularly 1.2 ⁇ It is preferably 10 15 ⁇ /sq or more, and more preferably 1.3 ⁇ 10 15 ⁇ /sq or more.
  • an electrostatic chuck table may be used as a support.
  • the surface of the dicing sheet on the base material side is brought into contact with the electrostatic chuck table, and the surface is electrostatically adsorbed to hold the dicing sheet.
  • the surface resistivity is 1.0 ⁇ 10 15 ⁇ /sq or more, the dicing sheet can be easily held well on the electrostatic chuck table.
  • the surface resistivity is preferably 1.0 ⁇ 10 16 ⁇ /sq or less.
  • the base material in the present embodiment is not particularly limited as long as it can achieve the above-mentioned mass reduction rate and has desired performance for performing plasma dicing.
  • the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive having an active energy ray-curable property, as described below, the base material is exposed to active energy rays irradiated for curing the pressure-sensitive adhesive layer. It is preferable that it has good transparency.
  • the substrate is preferably a resin film containing a resin-based material as a main material, and specific examples of such a material include polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, ethylene-norbornene copolymer, Polyolefin resin such as norbornene resin; propylene copolymer such as ethylene-polypropylene random copolymer; ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid methyl copolymer, other ethylene- Ethylene copolymers such as (meth)acrylic acid ester copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; ethylene-vinyl acetate copolymers; polyvinyl chloride, vinyl chloride copolymers And other polyvinyl chloride resins; (meth)acrylic acid ester copolymers; polyurethan
  • a polyolefin-based resin a polyolefin-based resin, a propylene-based copolymer, an ethylene-based copolymer, and a polyester-based resin from the viewpoint of easily achieving the above-mentioned mass reduction rate.
  • the base material may be a film made of one of the above-mentioned materials, or a film made of a plurality of the above-mentioned materials. Further, the base material may be a laminated film formed by laminating a plurality of such films. In this laminated film, the materials forming each layer may be the same or different.
  • the base material is a film made of the above-mentioned propylene-based copolymer and ethylene-based copolymer, from the viewpoint of easily achieving the above-mentioned mass reduction rate and easily achieving excellent expandability.
  • a film made of an ethylene-polypropylene random copolymer and an ethylene-(meth)acrylic acid copolymer is particularly preferable.
  • the ratio of the propylene-based copolymer and the ethylene-based copolymer is preferably 0.1 part by mass or more of the propylene-based copolymer with respect to 100 parts by mass of the ethylene-based copolymer. It is particularly preferable that the amount is 1 part by mass or more.
  • the amount of the propylene-based copolymer is preferably less than 5 parts by mass, and particularly preferably 4.5 parts by mass or less, relative to 100 parts by mass of the ethylene-based copolymer.
  • the base material is a film made of an ethylene-based copolymer as opposed to a film made of the propylene-based copolymer and the ethylene-based copolymer described above, from the viewpoint that it is easy to achieve more excellent expandability. It is particularly preferable that a film made of an ethylene-(meth)acrylic acid copolymer is laminated.
  • a layer formed of a film using a propylene-based copolymer and an ethylene-based copolymer as a material is conveniently referred to as a “first layer”, and an ethylene-based copolymer is used as a material.
  • the layer formed of the film will be referred to as "second layer".
  • the first layer and the second layer may include components other than those described above as materials.
  • the base material is a film made of an ethylene-(meth)acrylic acid copolymer and an epoxy compound, from the viewpoints of easily achieving the above-mentioned mass reduction rate and easily achieving excellent heat resistance. Good.
  • the film may contain a component other than the ethylene-(meth)acrylic acid copolymer and the epoxy compound as a material.
  • the epoxy compound may be a compound having an epoxy group in the molecule, preferably a compound having one or more epoxy groups, more preferably a compound having two or more epoxy groups, and particularly preferably two epoxy groups. Compounds are preferred.
  • the ratio of the ethylene-(meth)acrylic acid copolymer to the epoxy compound is ethylene-(meth)
  • the amount of the epoxy compound is preferably 0.05 parts by mass or more based on 100 parts by mass of the acrylic acid copolymer. Further, it is preferable that the amount of the epoxy compound is less than 0.3 part by mass based on 100 parts by mass of the ethylene-(meth)acrylic acid copolymer.
  • the base material may contain various additives such as a flame retardant, a plasticizer, an antistatic agent, a lubricant, an antioxidant, a colorant, an infrared absorber, an ultraviolet absorber and an ion scavenger.
  • a flame retardant such as a flame retardant, a plasticizer, an antistatic agent, a lubricant, an antioxidant, a colorant, an infrared absorber, an ultraviolet absorber and an ion scavenger.
  • the content of these additives is not particularly limited, but it is preferably within a range in which the base material exhibits a desired function.
  • the method for producing the base material in the present embodiment is not particularly limited, and examples thereof include melt extrusion methods such as T-die method and round die method; calendar method; solution method such as dry method and wet method. Above all, it is preferable to employ the melt extrusion method or the calender method from the viewpoint of efficiently producing the substrate.
  • melt extrusion methods such as T-die method and round die method
  • calendar method such as dry method and wet method.
  • solution method such as dry method and wet method.
  • the materials of the substrate are kneaded, and the obtained kneaded product is directly produced, or pellets are once produced, and then a film is formed using a known extruder. Good.
  • a base material composed of a plurality of layers is produced by a melt extrusion method
  • the components constituting each layer are kneaded, respectively, and directly from the obtained kneaded product or once pellets are produced, using a known extruder.
  • a plurality of layers may be simultaneously extruded to form a film.
  • the surface of the base material on which the pressure-sensitive adhesive layer is laminated may be subjected to a surface treatment such as a primer treatment, a corona treatment, or a plasma treatment in order to enhance the adhesion with the pressure-sensitive adhesive layer.
  • a surface treatment such as a primer treatment, a corona treatment, or a plasma treatment in order to enhance the adhesion with the pressure-sensitive adhesive layer.
  • the thickness of the base material is preferably 50 ⁇ m or more, particularly preferably 60 ⁇ m or more, and further preferably 70 ⁇ m or more. Further, the thickness of the base material is preferably 200 ⁇ m or less, particularly preferably 180 ⁇ m or less, and further preferably 150 ⁇ m or less. When the thickness of the base material is 50 ⁇ m or more, the dicing sheet tends to have appropriate strength, and breakage during use can be effectively suppressed. On the other hand, when the thickness of the base material is 200 ⁇ m or less, it becomes easy to effectively suppress the release of the volatile component originating from the base material when the dicing sheet is placed under a vacuum condition.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer in the present embodiment is not particularly limited as long as it can achieve the above-described mass reduction rate and has desired performance for performing plasma dicing.
  • the pressure-sensitive adhesive may be a pressure-sensitive adhesive that does not have active energy ray curability (active energy ray non-curable pressure-sensitive adhesive), or is a pressure-sensitive adhesive that has active energy ray curability (active energy ray-curable pressure-sensitive adhesive). It may be.
  • the content of the low molecular weight component in the pressure-sensitive adhesive layer is preferably relatively small from the viewpoint of easily achieving the above-described mass reduction rate. From this viewpoint, the pressure-sensitive adhesive layer is preferably an active energy ray non-curable pressure-sensitive adhesive.
  • Active energy ray non-curable pressure-sensitive adhesive As the active energy ray non-curable pressure-sensitive adhesive, those having desired adhesive strength and removability are preferable, for example, acrylic pressure-sensitive adhesive, rubber pressure-sensitive adhesive, Silicone-based adhesives, urethane-based adhesives, polyester-based adhesives, polyvinyl ether-based adhesives and the like can be used. Among these, it is preferable to use an acrylic pressure-sensitive adhesive from the viewpoint of easily achieving a desired adhesive force.
  • the acrylic pressure-sensitive adhesive as the active energy ray non-curable pressure-sensitive adhesive is preferably composed of the acrylic copolymer (a1) and the cross-linking agent (E).
  • the acrylic copolymer (a1) preferably contains a structural unit derived from a functional group-containing monomer and a structural unit derived from a (meth)acrylic acid ester monomer or a derivative thereof.
  • the functional group-containing monomer as a constituent unit of the acrylic copolymer (a1) has a polymerizable double bond and a functional group such as a hydroxy group, a carboxy group, an amino group, a substituted amino group, and an epoxy group in the molecule. It is preferable that the monomer has
  • hydroxy group-containing monomer examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Examples thereof include 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, which may be used alone or in combination of two or more kinds.
  • carboxy group-containing monomer examples include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid. These may be used alone or in combination of two or more.
  • carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid. These may be used alone or in combination of two or more.
  • amino group-containing monomer or the substituted amino group-containing monomer examples include aminoethyl (meth)acrylate and n-butylaminoethyl (meth)acrylate. These may be used alone or in combination of two or more.
  • the acrylic copolymer (a1) preferably contains the structural unit derived from the functional group-containing monomer in an amount of 1% by mass or more, particularly preferably 5% by mass or more, and further preferably 10% by mass or more. Preferably.
  • the acrylic copolymer (a1) preferably contains the structural unit derived from the functional group-containing monomer in an amount of 35% by mass or less, and particularly preferably 30% by mass or less.
  • Examples of the (meth)acrylic acid ester monomer constituting the acrylic copolymer (a1) include (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms, (meth)acrylic acid cycloalkyl ester, ( For example, benzyl meth)acrylate is used.
  • alkyl (meth)acrylates having an alkyl group with 1 to 18 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth ) N-butyl acrylate, 2-ethylhexyl (meth)acrylate and the like are used.
  • the acrylic copolymer (a1) preferably contains a structural unit derived from the (meth)acrylic acid ester monomer in an amount of 50% by mass or more, particularly preferably 60% by mass or more, and further 70% by mass. % Or more is preferable.
  • the acrylic copolymer (a1) preferably contains the structural unit derived from the (meth)acrylic acid ester monomer in an amount of 99% by mass or less, and particularly preferably in an amount of 95% by mass or less.
  • the acrylic copolymer (a1) can be obtained by copolymerizing a functional group-containing monomer as described above and a (meth)acrylic acid ester monomer or a derivative thereof by a conventional method. Dimethyl acrylamide, vinyl formate, vinyl acetate, styrene, etc. may be copolymerized.
  • the weight average molecular weight (Mw) of the acrylic copolymer (a1) is preferably 10,000 or more, particularly preferably 150,000 or more, and further preferably 200,000 or more.
  • the weight average molecular weight (Mw) is preferably 1.5 million or less, and particularly preferably 1 million or less.
  • the weight average molecular weight (Mw) in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).
  • a polyfunctional compound having reactivity with the functional group of the acrylic copolymer (a1) can be used as the cross-linking agent (E).
  • polyfunctional compounds include isocyanate compounds, epoxy compounds, amine compounds, melamine compounds, aziridine compounds, hydrazine compounds, aldehyde compounds, oxazoline compounds, metal alkoxide compounds, metal chelate compounds, metal salts, ammonium salts, Examples thereof include reactive phenol resins.
  • the blending amount of the crosslinking agent (E) is preferably 0.01 parts by mass or more, and particularly preferably 3 parts by mass or more, relative to 100 parts by mass of the acrylic copolymer (a1).
  • the amount of the cross-linking agent (E) compounded is preferably 20 parts by mass or less, and particularly preferably 17 parts by mass or less, relative to 100 parts by mass of the acrylic copolymer (a1).
  • the active energy ray-curable pressure-sensitive adhesive may be mainly composed of a polymer having an active energy ray-curable property, or an active energy ray-curable polymer.
  • the main component may be a mixture of (a polymer having no active energy ray curability) and a monomer and/or oligomer having at least one or more active energy ray curable groups.
  • the pressure-sensitive adhesive layer in the present embodiment is composed of an active energy ray-curable pressure-sensitive adhesive
  • the pressure-sensitive adhesive layer is cured by irradiation with active energy rays to reduce the adhesive strength of the dicing sheet to the adherend. be able to. This makes it possible to easily separate the obtained chip from the dicing sheet after the plasma dicing is completed.
  • the content of the low-molecular weight component in the pressure-sensitive adhesive layer is set to be relatively small, and thus, from the viewpoint of easily achieving the above-mentioned mass reduction rate, the active energy ray-curable pressure-sensitive adhesive that constitutes the pressure-sensitive adhesive layer.
  • the main component is a polymer having active energy ray curability.
  • the active energy ray-curable pressure-sensitive adhesive contains a polymer having active energy ray-curability as a main component will be described below.
  • the polymer having active energy ray curability is a (meth)acrylic acid ester (co)polymer (A) (hereinafter referred to as a (meth)acrylic acid ester (co)polymer in which a functional group having active energy ray curability (active energy ray curable group) is introduced into a side chain. It may be referred to as “active energy ray-curable polymer (A)”).
  • This active energy ray-curable polymer (A) comprises an acrylic copolymer (a1) having a functional group-containing monomer unit and an unsaturated group-containing compound (a2) having a functional group bonded to the functional group. It is preferably obtained by a reaction.
  • the acrylic copolymer (a1) having the functional group-containing monomer unit is a functional group-containing functional unit as a constituent unit in the acrylic copolymer (a1) described above as the material for the active energy ray non-curable pressure-sensitive adhesive. Those containing a monomer can be used.
  • the functional group contained in the unsaturated group-containing compound (a2) can be appropriately selected according to the type of functional group of the functional group-containing monomer unit contained in the acrylic copolymer (a1).
  • the functional group contained in the acrylic copolymer (a1) is a hydroxy group, an amino group or a substituted amino group
  • the functional group contained in the unsaturated group-containing compound (a2) is preferably an isocyanate group or an epoxy group.
  • the functional group contained in the copolymer (a1) is an epoxy group
  • the functional group contained in the unsaturated group-containing compound (a2) is preferably an amino group, a carboxy group or an aziridinyl group.
  • the unsaturated group-containing compound (a2) contains at least one active energy ray-polymerizable carbon-carbon double bond in one molecule, particularly 1 to 6, more preferably 1 to 4 carbon atoms. Is preferred. Specific examples of such unsaturated group-containing compound (a2) include, for example, 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1-( Bisacryloyloxymethyl)ethyl isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate; diisocyanate compound or polyisocyanate compound, polyol compound, (meth)acrylic Acryloyl monoisocyanate compound obtained by reaction with hydroxyethyl acid ester; glycidyl (me
  • the unsaturated group-containing compound (a2) is preferably 50 mol% or more, particularly preferably 60 mol% or more, and further preferably based on the number of moles of the functional group-containing monomer of the acrylic copolymer (a1). It is used in a proportion of 70 mol% or more.
  • the unsaturated group-containing compound (a2) is preferably 95 mol% or less, particularly preferably 93 mol% or less, based on the number of moles of the functional group-containing monomer of the acrylic copolymer (a1). It is preferably used in a proportion of 90 mol% or less.
  • the functional group of the acrylic copolymer (a1) and the functional group of the unsaturated group-containing compound (a2) Depending on the combination, the reaction temperature, pressure, solvent, time, presence or absence of catalyst, and type of catalyst can be appropriately selected. As a result, the functional group present in the acrylic copolymer (a1) reacts with the functional group in the unsaturated group-containing compound (a2), and the unsaturated group is replaced by the functional group in the acrylic copolymer (a1). It is introduced into the side chain to obtain an active energy ray-curable polymer (A).
  • the weight average molecular weight (Mw) of the active energy ray-curable polymer (A) thus obtained is preferably 10,000 or more, particularly preferably 150,000 or more, and more preferably 200,000 or more. Preferably.
  • the weight average molecular weight (Mw) is preferably 1.5 million or less, and particularly preferably 1 million or less.
  • the active energy ray-curable pressure-sensitive adhesive has a polymer having an active energy ray-curable property such as an active energy ray-curable polymer (A) as a main component
  • the active energy ray-curable pressure-sensitive adhesive is It may further contain a linear curable monomer and/or oligomer (B).
  • active energy ray-curable monomer and/or oligomer (B) for example, an ester of polyhydric alcohol and (meth)acrylic acid can be used.
  • Examples of the active energy ray-curable monomer and/or oligomer (B) include monofunctional acrylic acid esters such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene
  • Examples thereof include polyfunctional acrylic acid esters such as glycol di(meth)acrylate and dimethylol tricyclodecane di(meth)acrylate, polyester oligo(meth)acrylate, polyurethane oligo(meth)acrylate and the like.
  • the active energy ray-curable polymer (A) is blended with the active energy ray-curable monomer and/or oligomer (B), the active energy ray-curable monomer and/or Alternatively, the content of the oligomer (B) is preferably more than 0 parts by mass, and particularly preferably 60 parts by mass or more based on 100 parts by mass of the active energy ray-curable polymer (A). Further, the content is preferably 250 parts by mass or less, and particularly preferably 200 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable polymer (A).
  • UV rays when ultraviolet rays are used as active energy rays for curing the active energy ray-curable pressure-sensitive adhesive, it is preferable to add a photopolymerization initiator (C).
  • a photopolymerization initiator (C) Use of this photopolymerization initiator (C) Thereby, the polymerization and curing time and the light irradiation amount can be reduced.
  • photopolymerization initiator (C) examples include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2, 4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, ⁇ -chloranthraquinone, (2,4,6- Trimethylbenzyldiphenyl)phosphine oxide, 2-benzothiazole-N,N-diethyldithiocarbamate, oligo ⁇ 2-hydroxy-2-methyl-1-[4-(1
  • the photopolymerization initiator (C) is an active energy ray-curable polymer (A) (in the case of incorporating an active energy ray-curable monomer and/or oligomer (B), the active energy ray-curable polymer (A). ) And the total amount of the active energy ray-curable monomer and/or oligomer (B) 100 parts by mass) 0.1 parts by mass or more, particularly 0.5 parts by mass or more per 100 parts by mass. preferable. Further, the photopolymerization initiator (C) is an active energy ray-curable polymer (A) (in the case of incorporating an active energy ray-curable monomer and/or oligomer (B), an active energy ray-curable polymer).
  • the total amount of (A) and the active energy ray-curable monomer and/or oligomer (B) is 100 parts by mass) It is preferably used in an amount of 10 parts by mass or less, particularly 6 parts by mass or less, relative to 100 parts by mass.
  • the active energy ray-curable pressure-sensitive adhesive may appropriately contain other components.
  • other components include active energy ray non-curable polymer component or oligomer component (D), cross-linking agent (E), and the like.
  • Examples of the active energy ray non-curable polymer component or oligomer component (D) include polyacrylic acid ester, polyester, polyurethane, polycarbonate, polyolefin and the like, and a polymer having a weight average molecular weight (Mw) of 3,000 to 2,500,000 or Oligomers are preferred.
  • Mw weight average molecular weight
  • Oligomers are preferred.
  • the above-mentioned materials for the active energy ray non-curable pressure-sensitive adhesive can be used.
  • the pressure-sensitive adhesive layer is composed of an active energy ray-curable pressure-sensitive adhesive, and the active energy ray-curable pressure-sensitive adhesive has a polymer having active energy ray-curability as a main component
  • the compounding amount of the crosslinking agent (E) is It is preferably 0.01 part by mass or more, and particularly preferably 3 parts by mass or more, based on 100 parts by mass of the active energy ray-curable polymer (A).
  • the above-mentioned compounding amount is preferably 20 parts by mass or less, and particularly preferably 17 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable polymer (A).
  • the active energy ray-curable pressure-sensitive adhesive contains a mixture of an active energy ray-non-curable polymer component and a monomer and/or oligomer having at least one or more active energy ray-curable groups as main components, This will be described below.
  • the active energy ray non-curable polymer component for example, the same component as the above-mentioned acrylic copolymer (a1) can be used.
  • the same ones as the above-mentioned component (B) can be selected.
  • the compounding ratio of the active energy ray non-curable polymer component and the monomer and/or oligomer having at least one active energy ray curable group is at least 1 with respect to 100 parts by mass of the active energy ray non-curable polymer component.
  • the amount of the monomer and/or oligomer having one or more active energy ray-curable groups is preferably 1 part by mass or more, and particularly preferably 60 parts by mass or more.
  • the mixing ratio is preferably 200 parts by mass or less of a monomer and/or oligomer having at least one or more active energy ray-curable groups with respect to 100 parts by mass of the active energy ray non-curable polymer component, In particular, it is preferably 160 parts by mass or less.
  • the photopolymerization initiator (C) and the cross-linking agent (E) can be appropriately mixed.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m or more, particularly preferably 3 ⁇ m or more, and further preferably 5 ⁇ m or more. Moreover, the thickness of the pressure-sensitive adhesive layer is preferably 50 ⁇ m or less, particularly preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less. When the thickness of the pressure-sensitive adhesive layer is 1 ⁇ m or more, the dicing sheet can easily exhibit a desired pressure-sensitive adhesive force to the adherend. Moreover, when the thickness of the pressure-sensitive adhesive layer is 50 ⁇ m or less, it becomes easy to effectively suppress the release of the volatile component derived from the pressure-sensitive adhesive layer when the dicing sheet is placed under a vacuum condition. .. As a result, it is possible to effectively prevent unintentional peeling of the work from the dicing sheet during plasma dicing.
  • the surface of the pressure-sensitive adhesive layer opposite to the base material (hereinafter, may be referred to as “adhesive surface”) is attached to the work until the surface is attached.
  • a release sheet may be laminated on the surface for the purpose of protecting the.
  • the constitution of the release sheet is arbitrary, and an example is one in which a plastic film is release-treated with a release agent or the like.
  • Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
  • a silicone-based agent a fluorine-based agent, a long-chain alkyl-based agent, or the like can be used, and among these, a silicone-based agent that is inexpensive and can obtain stable performance is preferable.
  • the thickness of the release sheet is not particularly limited, but is usually 20 ⁇ m or more and 250 ⁇ m or less.
  • the adhesive layer may be laminated on the adhesive surface of the adhesive layer.
  • the dicing sheet according to the present embodiment can be used as a dicing/die bonding sheet by including the adhesive layer as described above.
  • a work is affixed to the surface of the adhesive layer opposite to the pressure-sensitive adhesive layer, and the adhesive layer is diced together with the work to laminate the individualized adhesive layers. You can get chips. The chip can be easily fixed to an object on which the chip is mounted by the individualized adhesive layer.
  • thermosetting adhesive component As a material for the above-mentioned adhesive layer, a material containing a thermoplastic resin and a low molecular weight thermosetting adhesive component, a material containing a B-stage (semi-cured) thermosetting adhesive component, or the like is used. It is preferable to use.
  • a protective film forming layer may be laminated on the adhesive surface of the adhesive layer.
  • the dicing sheet according to this embodiment can be used as a protective film-forming/dicing sheet.
  • a work is attached to the surface of the protective film forming layer opposite to the pressure-sensitive adhesive layer, and the protective film forming layer is diced together with the work, whereby the individual protective film forming layers are laminated.
  • the chip can be obtained.
  • a work having a circuit formed on one surface is preferably used, and in this case, usually, a protective film forming layer is laminated on the surface opposite to the surface on which the circuit is formed.
  • the protective film forming layer preferably comprises an uncured curable adhesive.
  • the method for manufacturing the dicing sheet according to this embodiment is not particularly limited, and is preferably manufactured by laminating the pressure-sensitive adhesive layer on one side of the base material.
  • the pressure-sensitive adhesive layer can be laminated on one side of the substrate by a known method.
  • a pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer, and optionally a coating liquid further containing a solvent or a dispersion medium are prepared, and the release-treated surface of the release sheet (hereinafter sometimes referred to as “release surface”).
  • the coating liquid is not particularly limited as long as it can be applied, and it may contain a component for forming the pressure-sensitive adhesive layer as a solute or a dispersoid.
  • the release sheet in this laminate may be released as a process material, or may be used to protect the adhesive surface of the adhesive layer until the dicing sheet is attached to the work.
  • the coating liquid for forming the pressure-sensitive adhesive layer contains a cross-linking agent
  • the cross-linking reaction may be allowed to proceed to form a cross-linked structure in the pressure-sensitive adhesive layer with a desired existing density.
  • the obtained dicing sheet is allowed to stand for several days in an environment of, for example, 23° C. and 50% relative humidity. You may carry out such a cure.
  • the pressure-sensitive adhesive layer may be directly formed on the substrate.
  • the pressure-sensitive adhesive layer is formed by applying the above-mentioned coating liquid for forming the pressure-sensitive adhesive layer on one side of the substrate to form a coating film, and drying the coating film.
  • the dicing sheet according to this embodiment can be used for plasma dicing.
  • the method of plasma dicing here is not particularly limited, and can be used for known plasma dicing.
  • a resist is laminated on a work to be diced by a general method to form a mask having a dicing line. Then, the pressure-sensitive adhesive layer side surface of the dicing sheet according to the present embodiment is bonded to the surface of the work opposite to the resist. The dicing sheet may be attached to the work before the resist is laminated on the work. Subsequently, the laminated body of the resist, the work, and the dicing sheet thus obtained is placed on a support table in a vacuum chamber of a plasma dicing apparatus. Then, plasma is generated in the vacuum chamber and the work is treated with the plasma through the resist, whereby the work is singulated along the above-mentioned dicing line.
  • the gas species for generating the plasma described above known ones can be used, but it is preferable to use SF 6 gas, for example.
  • the etching rate is preferably 0.05 ⁇ m/s or more, and particularly preferably 0.08 ⁇ m/s or more. Further, the etching rate is preferably 0.5 ⁇ m/s or less, and particularly preferably 0.4 ⁇ m/s or less.
  • the atmospheric pressure is preferably 0.1 MPa or less, and particularly preferably 0.05 MPa or less.
  • the table temperature is preferably 15° C. or higher, and particularly preferably 20° C. or higher. The table temperature is preferably 60°C or lower, and particularly preferably 50°C or lower.
  • the resist is removed by, for example, plasma treatment using O 2 gas. Then, a plurality of chips obtained by dividing the work into pieces are taken out from the vacuum chamber together with the dicing sheet, and then the chips are individually picked up from the dicing sheet and mounted on a predetermined substrate or the like.
  • a general work to be diced by plasma dicing can be used.
  • a semiconductor wafer a semiconductor member such as a semiconductor package, or a glass plate. And other glass members.
  • the dicing sheet according to the present embodiment can suppress the release of volatile components from the dicing sheet even when placed under the above-described vacuum conditions during plasma dicing. This makes it possible to prevent the volatile components from accumulating at the interface between the dicing sheet and the support table, and as a result, prevent unintended peeling of the dicing sheet from the support table. Therefore, by using the dicing sheet according to this embodiment, it is possible to perform good plasma dicing.
  • the dicing sheet according to the present embodiment satisfies the surface resistivity described above, it becomes easy to favorably hold the dicing sheet on the electrostatic chuck table. Therefore, in this case, it is preferable to use the dicing sheet for plasma dicing in which an electrostatic chuck table is used as a support.
  • the pressure-sensitive adhesive layer in the dicing sheet according to the present embodiment is composed of the active energy ray-curable pressure-sensitive adhesive as described above, the obtained chips are diced after the individualization of the work is completed. It is preferable to irradiate the pressure-sensitive adhesive layer in the dicing sheet with active energy rays before separating from the above. As a result, the pressure-sensitive adhesive layer is cured, and the adhesive force of the dicing sheet to the chip can be reduced, which facilitates separation of the chip from the dicing sheet.
  • an electromagnetic wave or a charged particle beam having an energy quantum can be used, and specifically, an ultraviolet ray, an electron beam or the like can be used.
  • ultraviolet rays which are easy to handle, are preferable. Irradiation of ultraviolet rays, a high-pressure mercury lamp, can be performed by a xenon lamp, LED, etc.
  • the dose of ultraviolet ray is illuminance 50 mW / cm 2 or more, and preferably 1000 mW / cm 2 or less.
  • the light amount is preferably at 50 mJ / cm 2 or more, particularly preferably at 80 mJ / cm 2 or more, and further preferably not 200 mJ / cm 2 or more.
  • the light amount is preferably at 10000 mJ / cm 2 or less, particularly preferably at 5000 mJ / cm 2 or less, and further preferably not 2000 mJ / cm 2 or less.
  • the electron beam irradiation can be performed by an electron beam accelerator or the like, and the electron beam irradiation amount is preferably 10 krad or more and 1000 krad or less.
  • another layer may be provided between the base material and the pressure-sensitive adhesive layer, or on the surface of the base material opposite to the pressure-sensitive adhesive layer.
  • Example 1 Preparation of pressure-sensitive adhesive composition 90 parts by mass of 2-ethylhexyl acrylate and 10 parts by mass of 2-hydroxyethyl acrylate were copolymerized by a solution polymerization method to prepare a (meth)acrylic acid ester polymer. .. When the molecular weight of this polymer was measured using gel permeation chromatography (GPC) described later, the weight average molecular weight (Mw) was 600,000.
  • GPC gel permeation chromatography
  • the coating liquid of the pressure-sensitive adhesive composition was prepared by mixing with 1 part by mass and diluting with ethyl acetate.
  • the obtained raw material for extrusion was extrusion-molded by a small T-die extruder (manufactured by Toyo Seiki Seisakusho, product name "Labo Plastomill”) to obtain a base material having a thickness of 100 ⁇ m.
  • the above-mentioned weight average molecular weight (Mw) is a standard polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC) (GPC measurement).
  • Example 2 95 parts by mass of n-butyl acrylate and 5 parts by mass of acrylic acid were copolymerized by a solution polymerization method to prepare a (meth)acrylic acid ester polymer.
  • Mw weight average molecular weight
  • a dicing sheet was obtained in the same manner as in Example 1 except that the pressure sensitive adhesive composition was used.
  • the pressure-sensitive adhesive layer in the obtained dicing sheet is composed of a pressure-sensitive adhesive having active energy ray curability.
  • Example 3 (1) Preparation of extrusion raw material for the first layer Ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., product name “Nucrel N0903HC", ratio of methacrylic acid-derived constitutional unit: 9% by mass, 23°C) Tensile modulus of elasticity at 140 MPa) and ethylene-polypropylene random copolymer (manufactured by Prime Polymer Co., product name “Prime Polypro F227D”, tensile modulus at 23° C.: 950 MPa, 230° C., MFR at 2.16 kgf load: 7.0 g/10 min, melting peak temperature: 135° C., heat of fusion: 81.9 J/g) with a mass ratio of 97:3, a twin-screw kneader (manufactured by Toyo Seiki Seisakusho, product name “Labo Plastomill”). ]) and the mixture was melt
  • Ethylene-methacrylic acid copolymer manufactured by Mitsui DuPont Polychemical Co., product name "Nucrel N0903HC", ratio of methacrylic acid-derived constituent units: 9% by mass, at 23°C
  • Tensile elastic modulus: 140 MPa was melt-kneaded with a twin-screw kneader (manufactured by Toyo Seiki Seisaku-sho, product name "Laboplast Mill”) to obtain an extrusion raw material B for the second layer.
  • a small T die extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was prepared by using the extrusion raw material A obtained in the step (1) and the extrusion raw material B obtained in the step (2).
  • Co-extrusion molding was performed by a product name “Labo Plastomill”) to obtain a base material having a two-layer structure including a first layer having a thickness of 40 ⁇ m and a second layer having a thickness of 60 ⁇ m.
  • Example 4 100 parts by mass of ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., product name “Nucrel N0903H, ratio of constituent units derived from methacrylic acid: 9% by mass) and bifunctional bisphenol A type epoxy resin (Japan Epoxy 0.25 parts by mass of resin, product name “jER1055”, number average molecular weight Mn: 1600) is melted at 210° C. with a twin-screw kneader (manufactured by Toyo Seiki Seisakusho, product name “Labo Plastomill”). Kneading was performed to obtain a raw material for extrusion.
  • ethylene-methacrylic acid copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd., product name “Nucrel N0903H, ratio of constituent units derived from methacrylic acid: 9% by mass
  • bifunctional bisphenol A type epoxy resin Japan Epoxy 0.
  • the obtained raw material for extrusion was extrusion-molded by a small-sized T-die extruder (manufactured by Toyo Seiki Seisakusho, product name “Labo Plastomill”) to obtain a base material having a thickness of 100 ⁇ m.
  • a dicing sheet was obtained in the same manner as in Example 1 except that the base material was used.
  • Example 5 A dicing sheet was obtained in the same manner as in Example 1 except that a polyethylene terephthalate film having a thickness of 100 ⁇ m (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”) was used as a substrate.
  • Example 2 A dicing sheet was obtained in the same manner as in Example 2 except that a vinyl chloride film having a thickness of 80 ⁇ m produced in the same manner as in Comparative Example 1 was used as a substrate.
  • Test Example 1 Measurement of mass reduction rate
  • the dicing sheets produced in the examples and comparative examples were cut into a size of 10 cm ⁇ 10 cm to obtain measurement samples.
  • the mass of the measurement sample was measured and used as the mass before vacuum conditions were applied.
  • the above-mentioned measurement sample is put into a vacuum low-temperature dryer (manufactured by Tokyo Rika Kikai Co., Ltd., product name “VOS-201SD”) set under vacuum conditions of an atmospheric pressure of 0.1 MPa and a temperature of 25° C., and under the vacuum conditions. Let stand for 60 minutes. Then, the measurement sample was taken out from the vacuum low temperature dryer, and the mass was measured again. The obtained mass was taken as the mass after the introduction of the vacuum conditions.
  • a vacuum low-temperature dryer manufactured by Tokyo Rika Kikai Co., Ltd., product name “VOS-201SD”
  • the dicing sheet with the silicon wafer adhered as described above was placed with the surface on the base side facing down. , Held by electrostatic adsorption.
  • the inside of the vacuum chamber is set to a vacuum condition with an atmospheric pressure of 0.03 MPa and a temperature of 25° C.
  • SF 6 gas is used as a plasma generating gas
  • a plasma is applied to the silicon wafer through the resist at an etching rate of 0.3 m/s.
  • the results are shown in Table 1.
  • ⁇ Plasma dicing was successfully performed without peeling of the dicing sheet from the electrostatic chuck table.
  • X Peeling of the dicing sheet from the electrostatic chuck table occurred, and plasma dicing could not be performed.
  • EMAA1 ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., product name “Nucrel N0908C", ratio of methacrylic acid-derived constitutional unit: 9% by mass)
  • EMAA2 ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., product name “Nucrel N0903HC”, ratio of methacrylic acid-derived constituent units: 9% by mass, tensile elastic modulus at 23° C.: 140 MPa)
  • Propylene copolymer ethylene-polypropylene random copolymer (manufactured by Prime Polymer Co., product name "Prime Polypro F227D”, tensile elastic modulus at 23°C: 950 MPa, 230°C, load 2.16 kgf, MFR: 7.0 g
  • the dicing sheets obtained in the examples were able to hold the work well when used for plasma dicing, thereby enabling good plasma dicing.
  • the dicing sheet of the present invention can be suitably used for plasma dicing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une feuille de découpage en dés pour découpage en dés au plasma pourvue d'un matériau de base et d'une couche adhésive qui est stratifiée sur un côté surface du matériau de base. Lorsque la feuille de découpage en dés pour découpage en dés au plasma est laissée au repos pendant 60 minutes sous l'environnement d'une pression atmosphérique de 0,1 MPa et à une température de 25 °C, le taux de diminution de masse de la feuille de découpage en dés pour découpage en dés au plasma est inférieur ou égal à 0,4 %. Selon cette feuille de découpage en dés pour découpage en dés au plasma, il est possible de supprimer le décollement de la feuille de découpage en dés d'une base de support au moment du découpage en dés au plasma.
PCT/JP2019/042095 2018-11-26 2019-10-28 Feuille de découpage en dés pour découpage en dés au plasma WO2020110548A1 (fr)

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WO2014142085A1 (fr) * 2013-03-11 2014-09-18 リンテック株式会社 Feuille adhésive, et procédés de production de composants associés à un dispositif traité
WO2016002975A1 (fr) * 2014-07-03 2016-01-07 リンテック株式会社 Feuille composite pour former un film de protection
JP2016171261A (ja) * 2015-03-13 2016-09-23 古河電気工業株式会社 ウェハ固定テープ、半導体ウェハの処理方法および半導体チップ
JP2017186521A (ja) * 2016-03-31 2017-10-12 三井化学株式会社 熱硬化性組成物、これを含む封止剤、有機ｅｌ素子用枠封止剤、及び有機ｅｌ素子用面封止剤、並びにその硬化物

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WO2022201656A1 (fr) * 2021-03-23 2022-09-29 リンテック株式会社 Film de matériau de base et feuille de traitement de pièce
JP7190610B1 (ja) * 2021-03-23 2022-12-15 リンテック株式会社 ワーク加工用シート

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