TW202104302A - Dicing tape and dicing die-bonding film - Google Patents

Abstract

Provided is a dicing tape or the like, which includes a base layer and an adhesive layer overlapping with the base layer, wherein the adhesive layer includes an acrylic polymer, the acrylic polymer includes a constitutional unit of C9-C11 alkyl (meth)acrylate and a constitutional unit of hydroxyl group-containing (meth)acrylate, and the acrylic polymer includes 40 mol% or more and 85 mol% or less of the constitutional unit of C9-C11 alkyl (meth)acrylate.

Description

Slicing tape, and slicing chip mucous film

The present invention relates to a dicing tape used in the manufacture of semiconductor integrated circuits, and a dicing die attach film provided with the dicing tape.

Previously, there are known dicing die films used in the manufacture of semiconductor integrated circuits. Such a dicing die bonding film includes, for example, a dicing tape and a die bonding layer laminated on the dicing tape and then on the wafer. The dicing tape has a substrate layer and an adhesive layer in contact with the die-bonding layer. Such a dicing die-bonding film is used in the manufacture of semiconductor integrated circuits in the following manner, for example.

The method of manufacturing a semiconductor integrated circuit usually includes: a step before a circuit surface is formed on a single side of a silicon wafer by a high-integration electronic circuit, and a step after the chip is cut out from the wafer with the circuit surface and assembled . The latter steps include, for example, the following steps: the mounting step, which is to attach the surface of the wafer on the opposite side to the circuit surface to the die-bonding layer, and fix the wafer to the dicing tape; the dicing step, which is processed by cutting The semiconductor wafers attached to the dicing tape through the die bonding layer are processed into smaller dies; the expansion step is to expand the distance between the smaller semiconductor chips that are processed; the picking step is to bond The wafer layer and the adhesive layer are peeled off, and the semiconductor chip (die) is taken out in the state where the die layer is attached; and the die bonding step is to adhere the semiconductor chip (die) in the state where the die layer is attached To be followed by the body. Semiconductor integrated circuits are manufactured through these steps. In the pick-up step of the above-mentioned manufacturing method, the cut semiconductor wafer and the die bonding layer corresponding to the size of the wafer in close contact with it are pushed up from the lower side of the dicing tape by the pin member of the pickup mechanism, and the self-cutting tape is Pick up. However, in recent years, as semiconductor products have become thinner and more compact, the thickness of semiconductor wafers has become thinner than before. If such a semiconductor wafer is used, the problem of deformation and breakage of the semiconductor wafer due to the above-mentioned lifting in the pickup step is more likely to occur. In order to prevent such damage, the dicing tape is required to be able to peel off the die-bonding film with a small amount of lift after cutting, that is, good pick-up properties.

In this regard, as a conventional chip adhesive film, for example, a known adhesive layer is provided with an adhesive composition containing a base polymer and a thermal crosslinking agent (Patent Document 1). In the diced wafer described in Patent Document 1, the adhesive layer has a gel fraction of less than 90% by mass before heating and a change in the gel fraction after heating of 90% by mass or more. The adhesive layer whose gel fraction becomes 90% by mass or more by heating can be easily peeled off from the adhesive crystal layer. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-278427

[The problem to be solved by the invention]

However, it cannot be said that sufficient research has been conducted on the diced die-cut film or die-cut tape that can provide good pick-up properties as described above.

Therefore, the subject of the present invention is to provide a dicing tape capable of achieving good pick-up properties and a dicing die bonding film capable of achieving good pick-up properties. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the dicing tape of the present invention is characterized in that: It is provided with a substrate layer and an adhesive layer overlapping the substrate layer, and The aforementioned adhesive layer contains acrylic polymer, The aforementioned acrylic polymer contains structural units of C9~C11 alkyl (meth)acrylates and structural units of hydroxyl-containing (meth)acrylates, The aforementioned acrylic polymer contains the structural units of the aforementioned (meth)acrylic acid C9~C11 alkyl ester of 40 mol% or more and 85 mol% or less. According to the dicing tape with the above structure, good pick-up properties can be exerted.

In the dicing tape of the present invention, it is preferable that the acrylic polymer includes 1 mol% or more and 30 mol% or less of the structural units of the hydroxyl-containing (meth)acrylate. With this, better pick-up properties can be exerted.

In the dicing tape of the present invention, it is preferable that the structural unit of the aforementioned hydroxyl-containing (meth)acrylate is the structural unit of the hydroxyl-containing (meth)acrylate C2-C4 alkyl ester. With this, better pick-up properties can be exerted.

In the dicing tape of the present invention, it is preferable that the aforementioned acrylic polymer further has a structural unit of (meth)acrylate containing a polymerizable group. With this, better pick-up properties can be exerted.

In the dicing tape of the present invention, it is preferable that the aforementioned acrylic polymer is calculated in molar ratio [C/(B+C)] with respect to the structural unit (B) of the aforementioned hydroxyl-containing (meth)acrylate and the aforementioned The polymerizable group-containing (meth)acrylate structural unit (C) includes the aforementioned polymerizable group-containing (meth)acrylate structural unit (C) 0.50 to 0.95. With this, better pick-up properties can be exerted.

The chip adhesive film of the present invention includes the above-mentioned chipping tape and a chip bonding layer laminated on the adhesive layer of the chipping tape. [Effects of Invention]

The dicing tape and the dicing chip adhesive film of the present invention have the effect of enabling good pick-up properties.

Hereinafter, one embodiment of the dicing die bonding film and the dicing tape of the present invention will be described with reference to the drawings.

As shown in FIG. 1, the dicing die-cutting film 1 of this embodiment includes a die-cutting tape 20 and an adhesive layer 22 laminated on the die-cutting tape 20 and a die-bonding layer 10 bonded to a semiconductor wafer.

The dicing tape 20 of this embodiment is usually a long piece, and is stored in a wound state before use. The dicing die sticking film 1 of this embodiment is pasted on an annular frame with an inner diameter that is one circle larger than that of the silicon wafer subjected to the slicing process, and then cut and used.

The dicing tape 20 of this embodiment includes a base layer 21 and an adhesive layer 22 overlapping the base layer 21. The adhesive layer 22 contains at least an acrylic polymer. The above-mentioned acrylic polymer has at least the structural unit of C9~C11 alkyl (meth)acrylate and the structural unit of hydroxyl-containing (meth)acrylate in the molecule. Furthermore, in this specification, the expression "(meth)acrylate" means at least one of methacrylate and acrylate. Similarly, the expression "(meth)acrylic acid" means at least one of methacrylic acid and acrylic acid.

In this embodiment, the adhesive layer 22 includes, for example, the above-mentioned acrylic polymer, isocyanate compound (crosslinking agent), and polymerization initiator.

The adhesive layer 22 preferably has a thickness of 3 μm or more and 200 μm or less. With the thickness of the adhesive layer 22 being 3 μm or more, the adhesion to the die bonding layer 10 can be made better. When the thickness of the adhesive layer 22 is 200 μm or less, the operability of the dicing tape 20 becomes better. The shape and size of the adhesive layer 22 are generally the same as the shape and size of the base layer 21.

In this embodiment, the above-mentioned acrylic polymer is composed of structural units of C9~C11 alkyl (meth)acrylates, structural units of (meth)acrylates containing hydroxyl groups, and (meth)acrylic acids containing polymerizable groups. The structural unit of the ester is composed. Furthermore, the structural unit is a unit constituting the main chain of the acrylic polymer. Each side chain in the above-mentioned acrylic polymer is contained in each structural unit constituting the main chain.

In the acrylic polymer contained in the adhesive layer 22, the above-mentioned structural units can be ^{analyzed by NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) such as 1} H-NMR, ¹³ C-NMR, and thermal decomposition GC/MS (Gas Chromatography). -Mass Spectrometry, gas chromatography mass spectrometry) analysis, and infrared spectroscopy to confirm. In addition, the molar ratio of the above-mentioned structural unit in the acrylic polymer is usually calculated from the compounding amount (addition amount) when the acrylic polymer is polymerized.

The structural unit of (meth)acrylic acid C9~C11 alkyl ester is derived from (meth)acrylic acid C9~C11 alkyl ester monomer. In other words, the molecular structure of the C9~C11 alkyl (meth)acrylate monomer after the polymerization reaction is the structural unit of the C9~C11 alkyl (meth)acrylate. In detail, the bonds generated by the polymerization reaction of (meth)acrylic acid C9~C11 alkyl ester monomers constitute a part of the main chain of the acrylic polymer. The expression "C9~C11 alkyl" means the carbon number of the hydrocarbon moiety ester-bonded to (meth)acrylic acid. In other words, (meth)acrylic acid C9~C11 alkyl ester monomer means a monomer formed by ester bonding of (meth)acrylic acid and an alcohol with 9 to 11 carbon atoms (usually a monohydric alcohol). The hydrocarbon part of the C9~C11 alkyl group may be a saturated hydrocarbon or an unsaturated hydrocarbon. For example, the hydrocarbon portion of the C9 to C11 alkyl group is linear saturated hydrocarbon, branched saturated hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon. The aforementioned hydrocarbon portion is preferably a linear saturated hydrocarbon or a branched saturated hydrocarbon, and more preferably a branched saturated hydrocarbon. Furthermore, the hydrocarbon portion of the C9~C11 alkyl group preferably does not contain a polar group containing oxygen (O) or nitrogen (N). This can suppress the extreme increase in the polarity of the alkyl polymer. Therefore, it is possible to prevent the adhesive layer 22 from having excessive affinity for the die bond layer 10. Therefore, the dicing tape 20 can be peeled off from the adhesive crystal layer 10 more satisfactorily.

As the structural unit of the C9~C11 alkyl (meth)acrylate, for example, n-nonyl (meth)acrylate, iso(second)nonyl (meth)acrylate, tertiary nonyl (meth)acrylate Esters, iso(meth)acrylate, n-decyl (meth)acrylate, iso(second) decyl (meth)acrylate, tertiary decyl (meth)acrylate, n-decyl (meth)acrylate Structural units of undecyl ester, iso(second) undecyl (meth)acrylate, and tertiary undecyl (meth)acrylate. The structural unit of C9~C11 alkyl (meth)acrylate is preferably at least one of the structural unit of nonyl (meth)acrylate and the structural unit of decyl acrylate, more preferably (meth)acrylic acid At least one of the structural unit of isononyl ester and the structural unit of isodecyl (meth)acrylate. In the alkyl (meth)acrylate structural unit, if the carbon number of the hydrocarbon moiety is 8 or less, the affinity between the adhesive layer 22 and the crystal bonding layer 10 is excessively increased, thereby making it difficult to self-adhere the dicing tape 20 The crystal layer 10 may be peeled off. In addition, if the carbon number of the hydrocarbon portion is 12 or more, the affinity between the adhesive layer 22 and the die bonding layer 10 is excessively reduced, which is useful in the manufacturing method of semiconductor integrated circuits (described in detail later). 20 The self-adhesive crystal layer 10 may be accidentally peeled off. The carbon number of the hydrocarbon part is particularly preferably 9 or 10.

The above-mentioned acrylic polymer contains the structural unit of (meth)acrylic acid C9~C11 alkyl ester (hereinafter, sometimes referred to as A component) 40 mol% or more and 85 mol% or less in the molecule. The above-mentioned acrylic polymer contains 40 mol% or more and 85 mol% or less of the structural units of C9~C11 alkyl (meth)acrylate, and therefore can exhibit good pick-up properties. The above-mentioned acrylic polymer more preferably contains 45 mol% or more of structural units of C9~C11 alkyl (meth)acrylate. Moreover, it is more preferable to contain 80 mol% or less.

The above-mentioned mol% is a value based on the monomer constituting the main chain of the acrylic polymer. In detail, the polymerization initiator or chain transfer agent incorporated into the main chain during the polymerization of the acrylic polymer is not considered in the above-mentioned mol%. Hereinafter, it is the same in the description. In other words, the above-mentioned acrylic polymer has a main chain formed by polymerizing the unsaturated double bond portion of the (meth)acrylic acid ester monomer in the (meth)acrylate monomer before polymerization. The above-mentioned mol% is the mole percentage relative to the total moles of the (meth)acrylate monomers constituting the main chain by polymerization. Furthermore, the molecular structure in the side chain of the acrylic polymer is not considered in the above-mentioned mol%.

The acrylic polymer has a structural unit of (meth)acrylate containing a hydroxyl group, and the hydroxyl group of the aforementioned structural unit easily reacts with an isocyanate group. By preliminarily coexisting an acrylic polymer having a structural unit of a hydroxyl-containing (meth)acrylate and an isocyanate compound in the adhesive layer 22, the adhesive layer can be appropriately polymerized. Therefore, the acrylic polymer can be sufficiently gelled. Therefore, the adhesive layer 22 can maintain the shape and exhibit adhesive performance.

The structural unit of the hydroxyl-containing (meth)acrylate is derived from the hydroxyl-containing (meth)acrylate monomer. In other words, the molecular structure of the hydroxyl-containing (meth)acrylate monomer after polymerization reaction is the structural unit of the hydroxyl-containing (meth)acrylate. Specifically, the bond produced by the polymerization reaction of the hydroxyl-containing (meth)acrylate monomer constitutes a part of the main chain of the acrylic polymer.

The structural unit of the hydroxyl-containing (meth)acrylate is preferably the structural unit of the hydroxyl-containing (meth)acrylate C2-C4 alkyl ester. The expression "C2~C4 alkyl" means the carbon number of the hydrocarbon moiety ester-bonded to (meth)acrylic acid. In other words, the hydroxyl-containing (meth)acrylic C2~C4 alkyl ester monomer refers to a monomer formed by ester bonding of (meth)acrylic acid and an alcohol with a carbon number of 2 to 4 (usually a dihydric alcohol). The hydrocarbon portion of the C2~C4 alkyl group is usually a saturated hydrocarbon. For example, the hydrocarbon portion of the C2~C4 alkyl group is a linear saturated hydrocarbon or a branched saturated hydrocarbon. The hydrocarbon portion of the C2~C4 alkyl group preferably does not contain a polar group containing oxygen (O) or nitrogen (N). Furthermore, in the structural unit of the hydroxyl-containing (meth)acrylate, the hydroxyl group (-OH group) can be bonded to any carbon (C) of the hydrocarbon moiety. The hydroxyl group (-OH group) is preferably bonded to the carbon (C) at the end of the hydrocarbon moiety.

As the structural unit of the hydroxyl-containing C2~C4 alkyl (meth)acrylate, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxyn-butyl (meth)acrylate can be mentioned. Or (meth) hydroxyisobutyl acrylate and other structural units of (meth) hydroxybutyl acrylate. Furthermore, in the structural unit of hydroxybutyl (meth)acrylate, the hydroxyl group (-OH group) can be bonded to the carbon (C) at the end of the hydrocarbon moiety, or can be bonded to the carbon (C) other than the end of the hydrocarbon moiety. Knot.

The structural unit of the hydroxyl-containing C2-C4 alkyl (meth)acrylate is not particularly limited. For example, it may be at least any one of hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate The structural unit, more specifically, may be a structural unit of at least any one of 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate.

The acrylic polymer preferably contains a hydroxyl-containing (meth)acrylate structural unit (hereinafter, sometimes referred to as component B) in the molecule by 1 mol% or more and 30 mol% or less. By containing 1 mol% or more of the structural unit of the hydroxyl-containing (meth)acrylate, there are more hydroxyl groups capable of undergoing a crosslinking reaction with the isocyanate compound (crosslinking agent). Therefore, the acrylic polymer can be sufficiently gelled by crosslinking. As a result, the fluidity of the adhesive layer 22 can be suppressed. Therefore, the adhesive layer 22 can maintain the shape and exhibit adhesive performance. Therefore, the adhesive force (before the pick-up step) of the adhesive layer 22 before irradiating active energy rays (ultraviolet rays, etc.) can be exhibited satisfactorily. The acrylic polymer more preferably contains 1.5 mol% or more of the structural unit of the hydroxyl-containing (meth)acrylate, and further preferably contains 2.0 mol% or more. In addition, by containing 30 mol% or less of the structural unit of the hydroxyl-containing (meth)acrylate, the polarity of the adhesive layer 22 can be suppressed to be low. Therefore, the polar interaction between the adhesive layer 22 and the die-bonding layer 10 is suppressed, and the dicing tape 20 can be peeled off from the die-bonding layer 10 more satisfactorily. Therefore, after irradiation with active energy rays (ultraviolet rays, etc.), better pick-up properties can be exhibited. The acrylic polymer is more preferably 20 mol% or less of the structural unit of the hydroxyl-containing (meth)acrylate, further preferably 17.5 mol% or less, and particularly preferably 10 mol% or less.

In this embodiment, the aforementioned acrylic polymer further contains a polymerizable group-containing (meth)acrylate structural unit as described above. In other words, the aforementioned acrylic polymer includes a structural unit of (meth)acrylate having a polymerizable unsaturated double bond in a side chain. Since the aforementioned acrylic polymer contains a polymerizable group-containing (meth)acrylate structural unit, the adhesive layer 22 can be cured by irradiation with active energy rays (ultraviolet rays, etc.) before the pickup step. Specifically, by irradiation with active energy rays such as ultraviolet rays, a photopolymerization initiator generates free radicals, and by the action of the free radicals, the acrylic polymers can undergo a crosslinking reaction with each other. Thereby, the adhesive force of the adhesive layer 22 can be reduced after irradiation than before irradiation. In addition, there is an advantage that the die bond layer 10 can be peeled off from the adhesive layer 22 well, and better pick-up properties can be exerted. Furthermore, as the active energy rays, ultraviolet rays, radiation rays, and electron beams can be used.

The structural unit of the (meth)acrylate containing a polymerizable group can be bonded to the structural unit of the (meth)acrylate containing a hydroxyl group with a monomer having a functional group and a polymerizable group that can be bonded to a hydroxyl group in the molecule. Knot formed. The above-mentioned functional group may also be an isocyanate group with higher reactivity with the hydroxyl group. In other words, the above-mentioned monomers may also have isocyanate groups and vinyl groups at both ends of the molecule. The vinyl group may also be a part of a (meth)acryloyl group, for example. Specifically, the structural unit of the polymerizable group-containing (meth)acrylate may have the hydroxyl group in the above-mentioned hydroxyl-containing (meth)acrylate structural unit and the isocyanate group-containing (meth)acrylate A molecular structure formed by urethane bonding of isocyanate groups of monomers. In other words, the structural unit of the (meth)acrylate containing the polymerizable group may also have the structural unit derived from the (meth)acrylate containing the hydroxyl group and polymerized via the urethane bond derived from the hydroxyl group. The molecular structure of the sex group ((meth)acryloyl group).

The structural unit of the polymerizable group-containing (meth)acrylate having a polymerizable group can be prepared after the polymerization of the acrylic polymer. For example, after the copolymerization of C9~C11 alkyl (meth)acrylate monomers and hydroxyl-containing (meth)acrylate monomers, one part of the structural units of the hydroxyl-containing (meth)acrylate can be The hydroxyl group and the isocyanate group of the isocyanate group-containing polymerizable monomer undergo a urethane reaction, thereby obtaining the above-mentioned polymerizable group-containing (meth)acrylate structural unit.

The aforementioned isocyanate group-containing (meth)acrylate monomer preferably has one isocyanate group and one (meth)acrylic acid group in the molecule. As said monomer, (meth)acrylic acid 2-isocyanato ethyl ester is mentioned, for example.

The above-mentioned acrylic polymer preferably contains a polymerizable group-containing (meth)acrylate structural unit (hereinafter, sometimes referred to as component C) in the molecule, 7.0 mol% or more, more preferably 7.5 mol% or more It is more preferable to contain 13.5 mol% or more. Moreover, it is preferable to contain 60 mol% or less of C component, it is more preferable to contain 54 mol% or less, and it is more preferable to contain 52 mol% or less.

The above-mentioned acrylic polymer preferably contains a hydroxyl group-containing (meth)acrylate structural unit and a polymerizable group-containing (meth)acrylate structural unit 15 mol% or more and 60 mol% or less in the molecule.

The above-mentioned acrylic polymer is preferably in terms of molar ratio [A/(B+C)] relative to the structural unit (B) of the hydroxyl-containing (meth)acrylate and the polymerizable group-containing (meth)acrylic acid The structural unit (C) of the ester includes the structural unit (A) of the C9~C11 alkyl (meth)acrylate from 0.5 to 6.0. When the above ratio [A/(B+C)] is 0.5 or more, it is possible to suppress excessive hardening of the adhesive layer 22 after irradiation with active energy rays (described in detail later). Therefore, the adhesive layer 22 can be deformed relatively easily when the cut semiconductor wafer and the die bonding layer 10 of the size equivalent to the wafer that are in close contact with the die are peeled from the dicing tape 20. Thereby, the peeling angle becomes more sufficient, and as a result, it can peel more favorable. In addition, since the above-mentioned ratio [A/(B+C)] is 6.0 or less, the adhesive layer 22 can be cured and contracted more satisfactorily after the active energy ray is irradiated. Therefore, the peeling force of the adhesive layer 22 to the die bond layer 10 is better reduced after irradiation. The aforementioned ratio [A/(B+C)] is more preferably 0.6 or more, still more preferably 0.67, and particularly preferably 0.7 or more. The aforementioned ratio [A/(B+C)] is more preferably 5.67 or less, still more preferably 5.5 or less, and particularly preferably 5.0 or less.

The above-mentioned acrylic polymer is preferably in terms of molar ratio [B/(B+C)] relative to the structural unit (B) of the hydroxyl-containing (meth)acrylate and the polymerizable group-containing (meth)acrylic acid The structural unit (C) of the ester and the structural unit (B) of the (meth)acrylate containing a hydroxyl group are 0.05 to 0.50. The aforementioned ratio [B/(B+C)] is more preferably 0.06 or more, and still more preferably 0.07 or more. The aforementioned ratio [B/(B+C)] is more preferably 0.40 or less, and still more preferably 0.20 or less.

The above-mentioned acrylic polymer is preferably in terms of molar ratio [C/(B+C)] relative to the structural unit (B) of the hydroxyl-containing (meth)acrylate and the polymerizable group-containing (meth)acrylic acid The structural unit (C) of the ester contains the structural unit (C) of the (meth)acrylate containing a polymerizable group from 0.50 to 0.95. When the above-mentioned ratio [C/(B+C)] is 0.50 or more, the adhesive layer 22 can be cured and contracted more sufficiently by the polymerization reaction accompanied by irradiation of ultraviolet rays or the like. Therefore, the peeling force when peeling the die-bonding layer 10 from the adhesive layer 22 can be reduced more sufficiently. In addition, by making the above-mentioned ratio [C/(B+C)] 0.95 or less, the number of hydroxyl groups that can react with the isocyanate compound (crosslinking agent) increases. Therefore, the acrylic polymers are cross-linked to each other, and gelation can be more adequately performed. As a result, the fluidity of the adhesive layer 22 is suppressed, and the adhesive layer 22 can maintain the shape and exhibit adhesive performance. The above-mentioned ratio [C/(B+C)] is more preferably 0.60 or more, and still more preferably 0.80 or more. The aforementioned ratio [C/(B+C)] is more preferably 0.95 or less, still more preferably 0.94 or less, and particularly preferably 0.93 or less.

The above-mentioned acrylic polymer preferably contains a hydroxyl-containing (meth)acrylate based on the molar ratio (B/A) relative to the structural unit (A) of the C9~C11 alkyl (meth)acrylate The structural unit (B) is 0.01 or more and 0.80 or less. When the above-mentioned ratio (B/A) is 0.01 or more, the number of hydroxyl groups that can react with the isocyanate compound (crosslinking agent) increases. Therefore, the acrylic polymers are cross-linked to each other and can be more fully gelled. As a result, the fluidity of the adhesive layer 22 is suppressed, and the adhesive layer 22 can maintain the shape and exhibit adhesive performance. With the above ratio (B/A) being 0.08 or less, the polarity of the adhesive layer 22 can be suppressed to be low. Therefore, the polar interaction between the adhesive layer 22 and the die-bonding layer 10 is suppressed, and the dicing tape 20 can be peeled off from the die-bonding layer 10 more satisfactorily. The above-mentioned ratio (B/A) is more preferably 0.02 or more, and still more preferably 0.03 or more. The aforementioned ratio (B/A) is more preferably 0.75 or less, and still more preferably 0.70 or less.

The above-mentioned acrylic polymer is preferably in terms of molar ratio (C/A), relative to the structural unit (A) of the C9~C11 alkyl (meth)acrylate, and contains a polymerizable group-containing (meth) The structural unit (C) of the acrylate is 0.08 or more and 1.40 or less. When the above-mentioned ratio (C/A) is 0.08 or more, the adhesive layer 22 can be cured and shrunk more sufficiently by irradiation with ultraviolet rays or the like, and the die-bonding layer can be peeled from the die-cutting tape 20 more satisfactorily. In addition, when the above-mentioned ratio (C/A) is 1.40 or less, it is possible to prevent the adhesive layer 22 from being excessively cured and contracted due to irradiation of ultraviolet rays or the like. Furthermore, if the excessive hardening and shrinkage of the adhesive layer 22 is suppressed, the adhesive layer 22 can be easily peeled from the dicing tape 20 when the cut semiconductor wafer and the adhesive layer corresponding to the size of the wafer in close contact with it are peeled off from the dicing tape 20 The ground is deformed. Thereby, the peeling angle becomes more sufficient, and as a result, it can peel more favorable. The above-mentioned ratio (C/A) is more preferably 0.09 or more, still more preferably 0.10 or more, and particularly preferably 0.20 or more. The aforementioned ratio (C/A) is more preferably 1.35 or less, still more preferably 1.30 or less, and particularly preferably 1.20 or less.

The above-mentioned acrylic polymer preferably contains a polymerizable group-containing (meth)acrylate relative to the structural unit (B) of the hydroxyl-containing (meth)acrylate in terms of molar ratio (C/B) The structural unit (C) is above 0.9 and below 18.0. When the above-mentioned ratio (C/B) is 0.9 or more, the adhesive layer 22 can be cured and contracted more sufficiently by irradiation with ultraviolet rays or the like, and the adhesive force of the adhesive layer 22 after irradiation can be reduced more sufficiently. Therefore, the die-bonding layer can be peeled off from the die-cutting tape 20 more satisfactorily. When the above-mentioned ratio (C/B) is 18.0 or less, the number of hydroxyl groups that can undergo a crosslinking reaction with the isocyanate compound (crosslinking agent) increases. Therefore, the acrylic polymer can be sufficiently gelled by crosslinking. As a result, the fluidity of the adhesive layer 22 is suppressed. Therefore, the adhesive layer 22 can maintain the shape and exhibit adhesive performance. The above-mentioned ratio (C/B) is more preferably 0.95 or more, and still more preferably 1.0 or more. The aforementioned ratio (C/B) is more preferably 17.5 or less, still more preferably 17.33 or less, and particularly preferably 17.0 or less.

In a preferred embodiment, the above-mentioned acrylic polymer comprises a structural unit of isononyl (meth)acrylate, a structural unit of (meth)acrylate containing a hydroxyl group, and a structure of (meth)acrylate containing a polymerizable group The unit, the structural unit of the hydroxyl-containing (meth)acrylate is at least one of the structural unit of hydroxyethyl (meth)acrylate or the structural unit of hydroxybutyl (meth)acrylate. In a further preferred embodiment, the structural unit of the (meth)acrylate containing a polymerizable group has a urethane formed by a partial hydroxyl group of the structural unit of the (meth)acrylate containing a hydroxyl group. The acid ester bond further has a (meth)acrylic acid group incorporated via the urethane bond as a polymerizable group.

The dicing tape 20 of this embodiment is provided with the adhesive layer 22 containing the acrylic polymer mentioned above. The adhesive layer 22 further contains an isocyanate compound (crosslinking agent). A part of the isocyanate compound may be in a state after being reacted by a urethane reaction or the like. The isocyanate compound has a plurality of isocyanate groups in the molecule. Since the isocyanate compound has a plurality of isocyanate groups in the molecule, the crosslinking reaction between the acrylic polymers in the adhesive layer 22 can proceed. Specifically, by reacting one part of the isocyanate group of the isocyanate compound with the hydroxyl group of the acrylic polymer, and the other part of the isocyanate group reacting with the hydroxyl group of the other acrylic polymer, the crosslinking reaction via the isocyanate compound can be carried out.

Examples of the isocyanate compound include diisocyanates such as aliphatic diisocyanates, alicyclic diisocyanates, and aromatic aliphatic diisocyanates.

Examples of aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene Diisocyanate, 2,6-diisocyanato methyl caproate, etc. As the alicyclic diisocyanate, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane, 1,3- or 1,4-bis(isocyanatomethyl ) Cyclohexane, methylcyclohexane-2,4- or 2,6-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3- or 1,4-diisocyanate Cyclohexane and so on. Examples of aromatic diisocyanates include m-phenylene diisocyanate or p-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4- or 2,6-toluene diisocyanate, 1,3' -Or 1,4-bis(isocyanatomethyl)benzene, 1,3- or 1,4-bis(α-isocyanatoisopropyl)benzene, etc.

Moreover, as an isocyanate compound, triisocyanate is mentioned. As the triisocyanate, for example, triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene, 1,3,5-tris(isocyanato Methyl)cyclohexane, 1,3,5-tris(isocyanatomethyl)benzene, 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl, etc. Furthermore, as the isocyanate compound, for example, polymeric polyisocyanates such as dimers and trimers of diisocyanates, and polymethylene polyphenylene polyisocyanates can be cited.

In addition, as an isocyanate compound, for example, a polyisocyanate obtained by reacting an excess of the above-mentioned isocyanate compound with an active hydrogen-containing compound is mentioned. Examples of the active hydrogen-containing compound include active hydrogen-containing low-molecular-weight compounds, active hydrogen-containing high-molecular-weight compounds, and the like. Examples of low molecular weight compounds containing active hydrogen include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, and new Pentylene glycol, hexanediol, cyclohexane dimethanol, cyclohexanediol, hydrogenated bisphenol A, benzenedimethanol, glycerin, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol Sugar alcohol (sorbitol), sorbit (sorbit), sucrose, castor oil, ethylenediamine, hexamethylenediamine, diethanolamine, triethanolamine, water, ammonia, urea, etc., as high molecular weight compounds containing active hydrogen, Examples include various polyether polyols, polyester polyols, polyurethane polyols, acrylic polyols, epoxy polyols, and the like.

Furthermore, as an isocyanate compound, allophanate polyisocyanate, biuret polyisocyanate, etc. can also be used. The above-mentioned isocyanate compounds can be used individually by 1 type or in combination of 2 or more types.

The aforementioned isocyanate compound is preferably a reactant of an aromatic diisocyanate and an active hydrogen-containing low molecular weight compound. The reactant of the aromatic diisocyanate has a relatively slow reaction speed of the isocyanate group, so the adhesive layer 22 containing the reactant can prevent excessive hardening. The above-mentioned isocyanate compound is preferably one having 3 or more isocyanate groups in the molecule.

The polymerization initiator contained in the adhesive layer 22 is a compound capable of starting the polymerization reaction by applying heat or light energy. Since the adhesive layer 22 contains a polymerization initiator, when heat or light energy is applied to the adhesive layer 22, the crosslinking reaction between the acrylic polymers can proceed. In detail, it is possible to start the polymerization reaction of the polymerizable groups between the acrylic polymers having the structural unit of the polymerizable group-containing (meth)acrylate, thereby hardening the adhesive layer 22. As a result, as described above, better pick-up properties can be exerted. As the polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or the like can be used. As the polymerization initiator, usual commercially available products can be used.

The adhesive layer 22 may further include other components in addition to the above-mentioned components. Examples of other components include: adhesion imparting agents, plasticizers, fillers, anti-aging agents, antioxidants, ultraviolet absorbers, light stabilizers, heat-resistant stabilizers, antistatic agents, surfactants, and light release agents Wait. The types and usage amounts of other ingredients can be appropriately selected according to the purpose.

The dicing tape 20 of the present embodiment includes a base layer 21 bonded to the above-mentioned adhesive layer 22. The base layer 21 is, for example, a metal foil, a fiber sheet such as paper or cloth, a rubber sheet, a resin film, or the like. The base material layer 21 may have a laminated structure. Examples of the fiber sheet constituting the base layer 21 include paper, woven fabric, non-woven fabric, and the like. As the material of the resin film, for example, polyolefin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer; ethylene-vinyl acetate copolymer (EVA), ionomer resin, ethylene-( Meth) acrylic copolymers, ethylene-(meth)acrylate (random, alternating) copolymers and other ethylene copolymers; polyethylene terephthalate (PET), polyethylene naphthalate (PEN) ), polybutylene terephthalate (PBT) and other polyesters; polyacrylate; polyvinyl chloride (PVC); polyurethane; polycarbonate; polyphenylene sulfide (PPS); aliphatic poly Polyamides, fully aromatic polyamides (aramid) and other polyamides; polyether ether ketone (PEEK); polyimine; polyether imine; polyvinylidene chloride; ABS (acrylonitrile-butane Olefin-styrene copolymer); cellulose or cellulose derivatives; polysiloxane-containing polymers; fluorine-containing polymers. These can be used individually by 1 type or in combination of 2 or more types.

When the base material layer 21 has a resin film, the resin film may be subjected to a stretching treatment or the like to control deformability such as elongation. For the surface of the base material layer 21, in order to improve the adhesion with the adhesive layer 22, surface treatment may also be performed. As the surface treatment, for example, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionized radiation treatment, and other oxidation treatments based on chemical or physical methods can be used. In addition, coating treatment based on coating agents such as thickening coating agents, primers, and adhesives may also be performed.

For the back side of the base layer 21 (the side that does not overlap with the adhesive layer 22), in order to impart releasability, for example, it may be coated with a release agent (release agent) such as silicone resin or fluorine resin. Cloth processing. The base layer 21 is preferably a light-transmitting (ultraviolet-transmitting) resin film or the like in terms of being able to apply active energy rays such as ultraviolet rays to the adhesive layer 22 from the back side.

The dicing tape 20 of this embodiment may be provided with a release sheet covering one surface of the adhesive layer 22 (the surface of the adhesive layer 22 that does not overlap the base layer 21) in the state before use. When the adhesive layer 10 having an area smaller than the adhesive layer 22 is arranged in a manner to be accommodated in the adhesive layer 22, the release sheet is arranged in a manner to cover both the adhesive layer 22 and the adhesive layer 10. The peeling sheet is used to protect the adhesive layer 22 and is peeled off before attaching the die bonding layer 10 to the adhesive layer 22.

As the release sheet, for example, a plastic film or paper that has been surface-treated with a release agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide can be used. In addition, as the release sheet, for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and chlorofluoroethylene-vinylidene fluoride copolymer can be used. Films made of fluorine-based polymers; films made of polyolefins such as polyethylene and polypropylene; films made of polyesters such as polyethylene terephthalate (PET). In addition, as the release sheet, for example, a plastic film or paper coated with a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate-based release agent can be used. Furthermore, the release sheet can be used as a support material for supporting the adhesive layer 22. The release sheet is particularly suitable for use when the adhesive layer 22 is stacked on the base layer 21. In detail, the adhesive layer 22 can be overlapped on the base layer 21 with the release sheet and the adhesive layer 22 laminated, and after the overlap, the release sheet is peeled off (transferred), thereby overlaying and adhering on the base layer 21剂层22。 Agent layer 22.

Next, the diced die attach film 1 of this embodiment will be described in detail.

The dicing die-cutting film 1 of this embodiment includes the above-mentioned die-cutting tape 20 and the die-cutting layer 10 laminated on the adhesive layer 22 of the die-cutting tape 20. The die bonding layer 10 is adhered to the semiconductor wafer during the manufacture of the semiconductor integrated circuit.

The die bonding layer 10 may include at least one of a thermosetting resin and a thermoplastic resin. The die bonding layer 10 preferably contains thermosetting resin and thermoplastic resin.

Examples of thermosetting resins include epoxy resins, phenol resins, amino resins, unsaturated polyester resins, polyurethane resins, silicone resins, thermosetting polyimide resins, and the like. As said thermosetting resin, only 1 type or 2 or more types can be used. In terms of containing fewer ionic impurities that may cause corrosion of the semiconductor wafer as the bonding target, the thermosetting resin is preferably an epoxy resin. As the hardener of epoxy resin, phenol resin is preferred.

Examples of the above epoxy resin include: bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, One of the sulphur type, phenol novolak type, o-cresol novolak type, trihydroxyphenylmethane type, tetraphenol ethane type, hydantoin type, triglycidyl isocyanurate type, or glycidylamine type Each epoxy resin. As the epoxy resin, a bisphenol A type epoxy resin is preferable in terms of being rich in reactivity with a phenol resin as a hardening agent and excellent in heat resistance.

Phenolic resin can act as a hardener for epoxy resin. As a phenol resin, polyoxystyrene, such as a novolak type phenol resin, a resol type phenol resin, polyparahydroxystyrene, etc. are mentioned, for example. As a novolak-type phenol resin, a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tertiary butylphenol novolak resin, a nonylphenol novolak resin, etc. are mentioned, for example. As the phenol resin, a phenol novolak resin is preferable, and a biphenol novolak resin is more preferable. When these phenol resins act as hardeners for epoxy resins (adhesives for die bonding), the adhesiveness of epoxy resins as adhesives can be further improved. As said phenol resin, only 1 type or 2 or more types can be used.

In the die-bonding layer 10, the hydroxyl group of the phenol resin is preferably 0.5 equivalent or more and 2.0 equivalent or less with respect to 1 equivalent of the epoxy group of the epoxy resin, and more preferably 0.7 equivalent or more and 1.5 equivalent or less. Thereby, the hardening reaction of the epoxy resin and the phenol resin can fully proceed.

When the die-bonding layer 10 contains thermosetting resin, the content ratio of the above-mentioned thermosetting resin in the die-bonding layer 10 relative to the total mass of the die-bonding layer 10 is preferably 5% by mass or more and 60% by mass or less, More preferably, it is 10% by mass or more and 50% by mass or less. Thereby, the die-bonding layer 10 can appropriately perform the function as a thermosetting adhesive.

As the thermoplastic resin that can be contained in the die-bonding layer 10, for example, natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene -Acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon (product name) or 6,6-nylon (product name), phenoxy Resin, acrylic resin, saturated polyester resin such as PET or PBT, polyimide resin, fluororesin, etc. As the above-mentioned thermoplastic resin, an acrylic resin is preferable in terms of having less ionic impurities and high heat resistance, so that the adhesiveness of the die-bonding layer 10 can be further ensured. As the above-mentioned thermoplastic resin, only one type or two or more types can be used.

The above-mentioned acrylic resin is preferably a polymer having the most structural units of alkyl (meth)acrylate in the structural units in the molecule in terms of mass ratio. Examples of the alkyl (meth)acrylate include C2 to C4 alkyl (meth)acrylate. The above-mentioned acrylic resin may also contain structural units derived from other monomer components copolymerizable with the alkyl (meth)acrylate monomer. Examples of the above-mentioned other monomer components include: carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, Functional group-containing monomers such as acrylamide and acrylonitrile, or various other multifunctional monomers. In terms of the higher cohesive force of the sticky layer 10, the acrylic resin is preferably an alkyl (meth)acrylate (especially an alkyl (meth)acrylate with a carbon number of 4 or less in the alkyl part). Base ester), carboxyl-containing monomers, nitrogen-containing monomers, and copolymers of multifunctional monomers (especially polyglycidyl-based multifunctional monomers), more preferably ethyl acrylate and butyl acrylate , Acrylic acid, acrylonitrile, and polyglycidyl (meth)acrylate copolymer.

In terms of the ease of setting the elasticity or viscosity of the die-bonding layer 10 within a desired range, the glass transition temperature (Tg) of the acrylic resin is preferably 5°C or more and 35°C or less, more preferably 10°C Above and below 30°C.

When the die-bonding layer 10 contains thermosetting resin and thermoplastic resin, the content ratio of the above-mentioned thermoplastic resin in the die-bonding layer 10 is relative to the organic components (e.g., thermosetting resin, thermoplastic resin, The total mass of hardening catalyst, etc., silane coupling agent, dye) is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less, and still more preferably 45% by mass or more and 55 mass% or less. Furthermore, by changing the content ratio of the thermosetting resin, the elasticity or viscosity of the die-bonding layer 10 can be adjusted.

When the thermoplastic resin of the die bond layer 10 has a thermosetting functional group, as the thermoplastic resin, for example, an acrylic resin containing a thermosetting functional group can be used. The acrylic resin containing a thermosetting functional group preferably contains a structural unit derived from an alkyl (meth)acrylate in the molecule at the largest mass ratio. As this (meth)acrylic acid alkyl ester, the (meth)acrylic acid (meth)alkyl ester exemplified above can be mentioned, for example. On the other hand, as a thermosetting functional group in the acrylic resin containing a thermosetting functional group, a glycidyl group, a carboxyl group, a hydroxyl group, an isocyanate group etc. are mentioned, for example. Among them, glycidyl is preferred. In other words, as the acrylic resin containing a thermosetting functional group, a glycidyl group-containing acrylic resin is preferable. The die bonding layer 10 preferably contains a thermosetting functional group-containing acrylic resin and a curing agent. Examples of the curing agent include those exemplified as the curing agent that can be contained in the adhesive layer 22. When the thermosetting functional group in the thermosetting functional group-containing acrylic resin is a glycidyl group, it is preferable to use a compound having a plurality of phenolic structures as the curing agent. For example, the various phenol resins mentioned above can be used as hardeners.

The crystal bonding layer 10 preferably contains a filler. By changing the amount of filler in the die-bonding layer 10, the elasticity and viscosity of the die-bonding layer 10 can be adjusted more easily. Furthermore, the electrical conductivity, thermal conductivity, and elastic modulus of the die-bonding layer 10 can be adjusted. Examples of fillers include inorganic fillers and organic fillers. As the filler, inorganic fillers are preferred. Examples of inorganic fillers include: aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, crystalline Filler of silicon dioxide such as silicon dioxide or amorphous silicon dioxide. In addition, as the material of the inorganic filler, simple metal such as aluminum, gold, silver, copper, and nickel, or alloys, etc. can be mentioned. It can also be fillers such as aluminum borate whiskers, amorphous carbon black, and graphite. The shape of the filler can be spherical, needle-like, flake-like and other shapes. As the filler, only one of the above-mentioned types or two or more types may be used.

The average particle diameter of the filler is preferably 0.005 μm or more and 10 μm or less, more preferably 0.005 μm or more and 1 μm or less. With the above-mentioned average particle size being 0.005 μm or more, the wettability and adhesiveness to adherends such as semiconductor wafers are further improved. When the above-mentioned average particle size is 10 μm or less, the characteristics brought about by the added filler can be more fully exhibited, and the heat resistance of the die-bonding layer 10 can be further exhibited. The average particle diameter of the filler can be determined using, for example, a photometric particle size distribution meter (for example, product name "LA-910", manufactured by Horiba Manufacturing Co., Ltd.).

When the die-bonding layer 10 contains a filler, the content ratio of the filler relative to the total mass of the die-bonding layer 10 is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less , More preferably 42% by mass or more and 55% by mass or less.

The die bonding layer 10 may also contain other components as needed. Examples of the above-mentioned other components include curing catalysts, flame retardants, silane coupling agents, ion scavengers, dyes, and the like. As the flame retardant, for example, antimony trioxide, antimony pentoxide, brominated epoxy resin, etc. may be mentioned. As the silane coupling agent, for example, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Group diethoxy silane and so on. As an ion scavenger, hydrotalcite, bismuth hydroxide, benzotriazole, etc. are mentioned, for example. As the above-mentioned other additives, only one type or two or more types may be used.

In terms of easy adjustment of elasticity and viscosity, the die-bonding layer 10 preferably includes a thermoplastic resin (especially an acrylic resin), a thermosetting resin, and a filler. In the die bond layer 10, the content ratio of the thermoplastic resin such as acrylic resin to the total mass of the organic components other than the filler is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass Hereinafter, it is more preferably 45% by mass or more and 55% by mass or less. Relative to the total mass of the die bond layer 10, the filler content is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less, and still more preferably 42% by mass or more and 55 Less than mass%.

The thickness of the die bond layer 10 is not particularly limited, and is, for example, 1 μm or more and 200 μm or less. The upper limit of the above thickness is preferably 100 μm, more preferably 80 μm. The lower limit of the aforementioned thickness is preferably 3 μm, more preferably 5 μm. Furthermore, when the die-bonding layer 10 is a laminated body, the above-mentioned thickness is the total thickness of the laminated body.

The glass transition temperature (Tg) of the die-bonding layer 10 is preferably 0°C or higher, more preferably 10°C or higher. When the above-mentioned glass transition temperature is 0° C. or higher, the adhesive layer 10 can be easily cut by cold expansion. The upper limit of the glass transition temperature of the die-bonding layer 10 is, for example, 100°C.

The die-bonding layer 10 may have a single-layer structure as shown in FIG. 1, for example. In this specification, a single layer means only a layer formed from the same composition. The form of a layered multilayer formed by the same composition is also a single layer. On the other hand, the sticky layer 10 may have, for example, a multilayer structure in which layers formed from two or more different compositions are laminated.

When the diced die sticking film 1 of this embodiment is used, the adhesive layer 22 is cured by, for example, irradiating ultraviolet rays. In detail, in a state where the die bonding layer 10 of a semiconductor wafer and the adhesive layer 22 attached to the other side of the die bonding layer 10 are laminated on one side, at least the adhesive layer 22 is irradiated with ultraviolet rays or the like. For example, ultraviolet rays and the like are irradiated from the side where the base material layer 21 is arranged, so that the ultraviolet rays and the like that have passed through the base material layer 21 reach the adhesive layer 22. The adhesive layer 22 is cured by irradiation with ultraviolet rays or the like. Since the adhesive layer 22 is hardened after irradiation, the adhesive force of the adhesive layer 22 can be reduced. Therefore, the die bond layer 10 (in the state where the semiconductor wafer is next) can be easily peeled off from the adhesive layer 22 after irradiation. In this way, good pick-up properties can be exerted.

The irradiation energy of active energy rays (ultraviolet rays, etc.) is at least 50 mJ/cm ² or more. The irradiation energy is, for example, 50 mJ/cm ² or more and 500 mJ/cm ² or less, preferably 100 mJ/cm ² or more and 300 mJ/cm ² or less. Usually, except for the peripheral part of the area where the adhesive layer 22 and the die bond layer 10 are bonded, active energy rays are irradiated. In the case of partial irradiation, irradiation is performed through a patterned photomask, thereby enabling the setting of unirradiated areas. In addition, it is possible to irradiate in dots to form an irradiated area. The device for irradiating ultraviolet rays is not particularly limited. For example, the product name "UM810" manufactured by Nitto Seiki Co., Ltd. can be used.

Before the active energy ray is irradiated, the peel strength (α) between the adhesive layer 22 and the die bond layer 10 is preferably 0.4 (N/20 mm) or more and 4.0 (N/20 mm) or less. On the other hand, after the active energy ray is irradiated, the peel strength (β) between the adhesive layer 22 and the die bond layer 10 is preferably 0.1 (N/20 mm) or less. The aforementioned peel strength (β) may be 0.03 (N/20 mm) or more. The ratio (α/β) of the peel strength between the adhesive layer 22 and the die bond layer 10 before (α) and after (β) irradiation of active energy rays is preferably 4.0 or more and 40.5 or less. Furthermore, the above-mentioned active energy ray irradiation was performed under the conditions described in the examples. In addition, the above-mentioned value related to peel strength was measured in accordance with the test conditions described in the examples.

In the chip adhesive film 1, the maximum strength when the peel strength between the adhesive layer 22 and the adhesive layer 10 is measured by the edge peel test after the irradiation of active energy rays is preferably 0.10 (N/10 mm) or more And 0.50 (N/10 mm) or less. Furthermore, the above-mentioned value related to the maximum strength of the edge peel test was measured according to the test conditions described in the examples.

The above-mentioned peeling strength (α or β) and the above-mentioned maximum strength can be increased by reducing the amount of filler contained in the die-bonding layer 10, for example.

The chip adhesive film 1 of the present embodiment may also be provided with a peeling sheet covering one side of the die bond layer 10 (the side of the die bond layer 10 that does not overlap the adhesive layer 22) in the state before use. The peeling sheet is used to protect the die-bonding layer 10 and is peeled off immediately before attaching the adherend (for example, a semiconductor wafer) to the die-bonding layer 10. As this release sheet, the same thing as the above-mentioned release sheet can be used. The release sheet can be used as a support material for supporting the die bond layer 10. The release sheet is suitable for use when overlaying the die bonding layer 10 on the adhesive layer 22. In detail, the die-bonding layer 10 can be overlapped on the adhesive layer 22 with the release sheet and die-bonding layer 10 laminated, and the release sheet can be peeled off (transferred) after the overlap, thereby superimposing and adhering on the adhesive layer 22晶层10。 Crystal layer 10.

Since the dicing die attach film 1 of this embodiment is configured as described above, it can exhibit good pick-up properties.

Next, the manufacturing method of the dicing tape 20 and the dicing die sticking film 1 of this embodiment will be described.

The manufacturing method of the dicing die sticking film 1 of this embodiment includes: The step of manufacturing the dicing tape 20 (the manufacturing method of the dicing tape), and the step of overlapping the die-bonding layer 10 on the manufactured dicing tape 20 to produce the dicing die-bonding film 1.

The manufacturing method of the dicing tape (the steps of manufacturing the dicing tape) has: Synthesis step, which is to synthesize acrylic polymer; The manufacturing step of the adhesive layer is to make the adhesive layer 22 by volatilizing the solvent from the adhesive composition containing the above-mentioned acrylic polymer, isocyanate compound, polymerization initiator, solvent, and other components suitably added according to the purpose; and In the laminating step, the adhesive layer 22 and the base material layer 21 are bonded together, thereby laminating the base material layer 21 and the adhesive layer 22.

In the synthesis step, for example, the C9~C11 (meth)acrylic acid C9~C11 alkyl ester monomer and the hydroxyl-containing (meth)acrylate monomer are subjected to free radical polymerization, thereby synthesizing the acrylic polymer intermediate. Free radical polymerization can be carried out by a usual method. For example, the above-mentioned monomers can be dissolved in a solvent and stirred while being heated, and a polymerization initiator can be added, thereby synthesizing an acrylic polymer intermediate. In order to adjust the molecular weight of the acrylic polymer, polymerization can also be carried out in the presence of a chain transfer agent. Secondly, a partial hydroxyl group of the structural unit of the hydroxyl group-containing (meth)acrylate contained in the acrylic polymer intermediate and the isocyanate group of the isocyanate group-containing polymerizable monomer are reacted by urethane formation. Bond. Thereby, a part of the structural unit of the (meth)acrylate containing a hydroxyl group is formed as a structural unit of the (meth)acrylate containing a polymerizable group. The urethane reaction can be carried out by a usual method. For example, in the presence of a solvent and a urethane catalyst, the acrylic polymer intermediate and the isocyanate group-containing polymerizable monomer are stirred while heating. Thereby, a part of the hydroxyl group of the acrylic polymer intermediate can be urethane-bonded with the isocyanate group of the isocyanate group-containing polymerizable monomer. In addition, in order to efficiently carry out the urethane reaction, the urethane reaction may be carried out in the presence of a Sn catalyst or the like.

In the adhesive layer preparation step, for example, an acrylic polymer, an isocyanate compound, and a polymerization initiator are dissolved in a solvent to prepare an adhesive composition. By changing the amount of solvent, the viscosity of the composition can be adjusted. Next, the adhesive composition is applied to the release sheet. As the coating method, for example, ordinary coating methods such as roll coating, screen coating, and gravure coating are used. The coated composition is subjected to solvent removal treatment or curing treatment, thereby curing the coated adhesive composition, and the adhesive layer 22 is produced. The solvent removal treatment is performed, for example, under conditions of 80°C or higher and 150°C or lower, 0.5 minutes or longer and 5 minutes or shorter.

In the layering step, the adhesive layer 22 and the base material layer 21 in a state of being overlapped with the release sheet are stacked and laminated. Furthermore, the release sheet may be in a state overlapping with the adhesive layer 22 until before use. Furthermore, in order to promote the reaction between the crosslinking agent and the acrylic polymer, and in order to promote the reaction between the crosslinking agent and the surface portion of the base layer 21, it is also possible to perform 48 hours at 50°C after the lamination step. Aging treatment steps. Furthermore, a commercially available film or the like may be used for the base layer 21, or it may be produced by forming a film by a normal method. As a method of film formation, for example, a calendering film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T die extrusion method, a co-extrusion method, a dry lamination method, etc. can be mentioned.

Through these steps, the dicing tape 20 can be manufactured.

The manufacturing method of chip adhesive film (the step of manufacturing chip adhesive film) includes: The resin composition preparation step, which is to prepare the resin composition used to form the die-bonding layer 10; The die-bonding layer manufacturing step, which is to make the die-bonding layer 10 from the resin composition; and The attaching step is to attach the adhesive layer 10 to the adhesive layer 22 of the dicing tape 20 manufactured as described above.

In the resin composition preparation step, for example, epoxy resin, epoxy resin curing catalyst, acrylic resin, phenol resin, solvent, etc. are mixed and each resin is dissolved in the solvent, thereby preparing the resin composition. By changing the amount of solvent, the viscosity of the composition can be adjusted. Furthermore, as these resins, commercially available products can be used.

In the manufacturing step of the die-bonding layer, for example, the resin composition prepared as described above is applied to the release sheet. The coating method is not particularly limited. For example, ordinary coating methods such as roll coating, screen coating, and gravure coating can be used. Next, as necessary, the applied composition is cured by solvent removal treatment or hardening treatment, etc., to produce the crystal bonding layer 10. The solvent removal treatment is performed, for example, under the conditions of 70° C. or higher and 160° C. or lower, 1 minute or longer and 5 minutes or shorter.

In the attaching step, the adhesive layer 22 and the die-bonding layer 10 of the die-cutting tape 20 respectively peel off the release sheet, and the die-bonding layer 10 and the adhesive layer 12 are attached in such a way that the die-bonding layer 10 and the adhesive layer 12 are in direct contact. For example, it can be bonded by crimping. The temperature at the time of bonding is not particularly limited, and is, for example, 30°C or higher and 50°C or lower, preferably 35°C or higher and 45°C or lower. The linear pressure during bonding is not particularly limited, but is preferably 0.1 kgf/cm or more and 20 kgf/cm or less, more preferably 1 kgf/cm or more and 10 kgf/cm or less.

The diced die attach film 1 manufactured as described above is used, for example, as an auxiliary tool for manufacturing semiconductor integrated circuits. The following describes specific examples in use.

The method of manufacturing a semiconductor integrated circuit usually includes a step of cutting out the wafer from the semiconductor wafer on which the circuit surface is formed and then assembling it. This step includes, for example, the following steps: a half-cutting step, in order to process the semiconductor wafer into a die by a slicing process, forming a groove in the semiconductor wafer, and then grinding the semiconductor wafer to reduce the thickness; the mounting step, which One side of the semi-cut semiconductor wafer (for example, the side opposite to the circuit surface) is attached to the die bonding layer 10, and the semiconductor wafer is fixed to the die dicing tape 20; the expansion step is to make the die The distance between the semi-cut semiconductor chips is enlarged; the pickup step is to peel off the die bond layer 10 and the adhesive layer 22 and take out the semiconductor die with the die bond layer 10 attached; and The die bonding step is to attach the semiconductor die with the die bonding layer 10 attached to the bonded body. When performing these steps, the dicing tape (chip slicing film) of this embodiment is used as a manufacturing auxiliary tool. In the half-cutting step, as shown in FIGS. 2A to 2D, a half-cutting process for cutting the semiconductor integrated circuit into dies is performed. Specifically, the wafer processing tape T is attached to the surface of the semiconductor wafer on the opposite side to the circuit surface. In addition, the dicing ring R is attached to the tape T for wafer processing. In the state where wafer processing tape T is attached, grooves for dividing are formed. The back polishing tape G is attached to the surface where the grooves are formed, and on the other hand, the wafer processing tape T that has been attached is peeled off. In the state where the back grinding tape G is attached, the grinding process is performed until the semiconductor wafer reaches a specific thickness. In the mounting step, as shown in FIGS. 3A to 3B, after the dicing ring R is mounted on the adhesive layer 22 of the dicing tape 20, a semi-cut semiconductor crystal is attached to the exposed surface of the die bonding layer 10 round. After that, the back polishing tape G is peeled off from the semiconductor wafer. In the expansion step, as shown in FIGS. 4A to 4C, the dicing ring R is fixed to the holder H of the expansion device. The lifting member U included in the expansion device is raised from the lower side of the dicing die attach film 1, thereby extending the dicing die attach film 1 so that it expands in the plane direction. In this way, the semi-cut semiconductor wafer is cut under specific temperature conditions. The above-mentioned temperature conditions are, for example, -20 to 5°C, preferably -15 to 0°C, more preferably -10 to -5°C. The lifting member U is lowered, thereby releasing the expanded state. Furthermore, in the expanding step, as shown in FIGS. 5A to 5B, the dicing tape 20 is expanded under a higher temperature condition to expand the area. Thereby, the adjacent semiconductor wafers that have been cut are pulled apart along the surface direction of the film surface, thereby expanding the gap. In the pick-up step, as shown in FIG. 6, the semiconductor wafer in the state where the die-bonding layer 10 is attached is peeled from the adhesive layer of the die-cutting tape 20. Specifically, the pin member P is raised, and the semiconductor wafer to be picked up is pushed up via the dicing tape 20. The lifted semiconductor chip is held by the suction jig J. In the die bonding step, the semiconductor chip in the state where the die bonding layer 10 is attached is attached to the adherend.

The matters disclosed in this manual include the following. (1) A dicing tape, which is provided with a substrate layer and an adhesive layer overlapping the substrate layer, and The aforementioned adhesive layer contains acrylic polymer, The aforementioned acrylic polymer contains structural units of C9~C11 alkyl (meth)acrylates and structural units of hydroxyl-containing (meth)acrylates, The aforementioned acrylic polymer contains the structural units of the aforementioned (meth)acrylic acid C9~C11 alkyl ester of 40 mol% or more and 85 mol% or less. (2) The dicing tape as described in the above (1), wherein the acrylic polymer includes 1 mol% or more and 30 mol% or less of the structural units of the hydroxyl-containing (meth)acrylate. (3) The dicing tape described in (2) above, wherein the structural unit of the hydroxyl-containing (meth)acrylate is the structural unit of the hydroxyl-containing (meth)acrylate C2-C4 alkyl ester. (4) The dicing tape described in any one of (1) to (3) above, wherein the structural unit of the aforementioned C9~C11 alkyl (meth)acrylate is the structural unit of nonyl (meth)acrylate and decyl acrylate At least one of the structural units of the ester. (5) The dicing tape described in any one of (1) to (4) above, wherein the acrylic polymer is measured in molar ratio (B/A) relative to the C9~C11 alkyl group of (meth)acrylic acid. The structural unit (A) of the ester includes the structural unit (B) of the aforementioned hydroxyl-containing (meth)acrylate from 0.01 to 0.80. (6) The dicing tape described in any one of (1) to (5) above, wherein the acrylic polymer further has a polymerizable group-containing (meth)acrylate structural unit. (7) The dicing tape described in the above (6), wherein the structural unit of the polymerizable group-containing (meth)acrylate has the hydroxyl group in the structural unit of the hydroxyl-containing (meth)acrylate and the isocyanate-containing group The isocyanate group of the (meth)acrylate monomer is a molecular structure formed by urethane bonding. (8) The dicing tape as described in the above (6) or (7), wherein the acrylic polymer contains the structural unit of the hydroxyl-containing (meth)acrylate and the polymerizable group-containing (meth) in the molecule The structural unit of acrylate is 15 mol% or more and 60 mol% or less. (9) The dicing tape described in any one of (6) to (8) above, wherein the acrylic polymer contains 7.0 mol% or more of the structural unit of the polymerizable group-containing (meth)acrylate in the molecule, and Below 60 mol%. (10) The dicing tape as described in any one of (6) to (9) above, wherein the acrylic polymer is measured in molar ratio (C/A) relative to the C9~C11 alkyl group of (meth)acrylic acid. The structural unit (A) of the ester includes the structural unit (C) of the polymerizable group-containing (meth)acrylate of 0.08 or more and 1.40 or less. (11) The dicing tape described in any one of (6) to (10) above, wherein the acrylic polymer is based on molar ratio (C/B), relative to the hydroxyl-containing (meth)acrylate The structural unit (B) includes the structural unit (C) of the polymerizable group-containing (meth)acrylate of 0.9 or more and 18.0 or less. (12) The dicing tape described in any one of (6) to (11) above, wherein the acrylic polymer is calculated in molar ratio [A/(B+C)] relative to the hydroxyl-containing (meth)acrylic acid The structural unit (B) of the ester and the structural unit (C) of the aforementioned polymerizable group-containing (meth)acrylate, including the structural unit (A) of the aforementioned (meth)acrylate C9~C11 alkyl ester 0.5 or more and 6.0 the following. (13) The dicing tape described in any one of (6) to (12) above, wherein the acrylic polymer is based on molar ratio [C/(B+C)] relative to the hydroxyl-containing (meth)acrylic acid The structural unit (B) of the ester and the structural unit (C) of the (meth)acrylate containing the polymerizable group, including the structural unit of the (meth)acrylate containing the polymerizable group (C) 0.50 or more and 0.95 the following. (14) The dicing tape described in any one of (1) to (13) above, wherein the adhesive layer includes the acrylic polymer, an isocyanate compound, and a polymerization initiator. (15) A dicing chip adhesive film comprising: the dicing tape as described in any one of (1) to (14) above, and a crystal sticking layer laminated on the aforementioned adhesive layer of the dicing tape. (16) The die-cut die-bonding film described in (15) above, wherein the die-bonding layer includes at least one of a thermosetting resin and a thermoplastic resin, and a filler.

The dicing tape and dicing adhesive film of this embodiment are as exemplified above, but the present invention is not limited to the dicing tape and dicing adhesive film exemplified above. That is, various forms used in ordinary dicing tapes and dicing sticky films can be adopted within the range that does not impair the effects of the present invention. [Example]

Next, the present invention will be explained in more detail with experimental examples, but the present invention is not limited to these.

The dicing tape is manufactured in the following manner. In addition, the dicing tape is used to produce a dicing die sticking film.

＜Raw material of acrylic polymer＞ "The first synthesis stage" •(Meth)acrylate C9~C11 alkyl ester: Isodecyl acrylate (IDA) • (Meth) acrylic acid C9~C11 alkyl ester: isononyl acrylate (INA) •Hydroxy-containing (meth)acrylate: 2-hydroxyethyl acrylate (HEA) • (Meth) acrylate containing hydroxyl group: 4-hydroxybutyl acrylate (4HBA) •Polymerization initiator: azobisisobutyronitrile (AIBN) •Polymerization solvent: ethyl acetate "Second Synthesis Stage": Preparation of structural units of (meth)acrylate containing polymerizable groups •Isocyanate group-containing (meth)acrylate monomer: 2-isocyanatoethyl methacrylate (product name "KarenzMOI" manufactured by Showa Denko) •Carbamate reaction catalyst: dibutyltin dilaurate ＜Raw material of crystal cut tape＞ • Adhesive layer Acrylic polymer (synthesized separately) Isocyanate compound The ethyl acetate solution of the trimethylolpropane adduct of toluene diisocyanate (product name "CORONATE L" manufactured by Tosoh Corporation) Photopolymerization initiator (product name "Omnirad127" manufactured by IGM Resins) •Substrate layer EVA film (corona treatment after film formation) The product name "Evaflex V1010" resin (manufactured by Mitsui DuPont Chemical Co., Ltd.) is formed into a film with a thickness of 125 μm without stretching, and the surface in contact with the adhesive layer is corona treated. •Organic solvent (used when making adhesive layer) Ethyl acetate

(Example 1) After synthesizing the acrylic polymer intermediate in the following manner, the acrylic polymer is synthesized from the acrylic polymer intermediate. Synthetic acrylic polymer is used to make adhesive layer to make dicing tape. "The first synthesis stage: the synthesis of acrylic polymer intermediates" The above-mentioned raw materials were mixed in the amounts (parts by mass) shown in Table 1 to prepare a mixture. The 1 L round bottom separable flask is equipped with a separable cap, a separatory funnel, a thermometer, a nitrogen introduction tube, a Liebig condenser, a vacuum sealing device (Vacuumseal), a stirring rod, and a stirring blade. The experimental device for polymerization Add the above mixture. While stirring, perform nitrogen replacement at room temperature for 6 hours. Thereafter, while flowing nitrogen gas, the mixture was stirred and maintained at 62°C for 3 hours, and thereafter maintained at 75°C for 2 hours. Thereby, the polymerization reaction is carried out, and it is cooled to room temperature to obtain a polymer solution (a solution containing the base polymer of each acrylic polymer). "Second Synthesis Stage: Synthesis of Acrylic Polymers" To the obtained polymer solution (solution containing the acrylic polymer intermediate) was added 2-isocyanatoethyl methacrylate as a polymerizable (meth)acrylate monomer in the amount shown in Table 1 ( The product name is "Karenz MOI" (manufactured by Showa Denko Corporation) and dibutyltin dilaurate IV (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred at 50°C for 24 hours in an air atmosphere. "Preparation of composition for adhesive layer" The isocyanate compound [CORONATE L] and the photopolymerization initiator (Omnirad 127) in the amounts shown in Table 5 were mixed with respect to 100 parts by mass of the solid content of the acrylic polymer. Ethyl acetate as a dilution solvent was added, and the composition for an adhesive layer was prepared so that the content rate of a solid content might become 20 mass %. "Making of Adhesive Layer" As a release sheet, a PET film (product name "DIAFOIL MRF38" manufactured by Mitsubishi Chemical Corporation) was prepared. A mold release treatment was applied to one side of the film. The adhesive layer composition prepared as described above is applied to the surface of the release sheet subjected to the release treatment. The coated composition was dried on the release sheet at 120°C for 3 minutes to form an adhesive layer with a thickness of 10 μm. "Manufacturing of Cut Strips" In the state where the adhesive layer and the release sheet are overlapped, the adhesive layer is attached to the corona treated surface of the base layer (EVA film) without air bubbles. Drying treatment is carried out at 50°C for 48 hours to produce diced wafers.

＜Manufacturing of slicing and sticking film＞ •The production of the sticky layer Use the following raw materials to make the bonding layer in the following manner (the same ones are used in the examples and comparative examples) Acrylic resin: 100 parts by mass (Product name "TEISAN RESIN SG-P3", manufactured by Nagase ChemteX) Glass transition temperature 12℃, epoxy group included), Epoxy resin: 46 parts by mass (Product name "JER1001", manufactured by Mitsubishi Chemical Corporation) Bisphenol A type epoxy resin, Phenolic resin: 51 parts by mass (Product name "MEH-7851ss", manufactured by Meiwa Chemical Co., Ltd.) Biphenol novolac resin, Spherical silica: 191 parts by mass (Product name "SO-25R", manufactured by ADMATECHS), Hardening catalyst: 0.6 parts by mass (Product name "Curesol 2PHZ", manufactured by Shikoku Chemical Industry Co., Ltd.) The above-mentioned raw materials and methyl ethyl ketone were mixed to prepare a resin composition with a solid content concentration of 20% by mass. This resin composition was applied to one surface of a release sheet (PET thickness 50 μm). In addition, the coated surface was treated with silicone in advance. Heat at 130°C for 2 minutes to volatilize the solvent to form a sticky crystal layer with a thickness of 10 μm.

•Adhesion of the die bonding layer and the die cutting tape The die-bonding layer in the state of overlapping with the peeling sheet and the adhesive layer of the dicing tape after the peeling sheet is peeled off are bonded together so as not to mix in air bubbles. The die-bonding layer is arranged at the predetermined position of the wafer, and has a size that is 5 mm larger in diameter than the wafer size. Laminator is used for laminating to produce a diced die sticking film in a state where the adhesive layer and die bonding layer that are attached to each other are arranged between the substrate layer and the peeling sheet. In this state, a film obtained by standing for 24 hours at a temperature of 18-25°C, a humidity of 40-60%, and a light-shielding condition is used as a test sample.

(Examples 2~15) According to the blending compositions shown in Table 1 to Table 3 and Table 5, the dicing tape and the dicing sticky film were produced in the same manner as in Example 1.

(Comparative Examples 1 to 8) According to the compounding composition shown in Table 4 and Table 5, the dicing tape and the dicing die sticking film were produced in the same manner as in Example 1.

The blending compositions of the dicing tape and the dicing sticky film used in the production of the examples and comparative examples are shown in Tables 1 to 5.

[Table 1] Unit: parts by mass The first synthesis stage Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 INA 121.15 121.15 105.97 105.97 173.01 173.01 HEA 106.39 106.39 - - 54.54 54.54 4HBA - - 115.59 115.59 - - AIBN 0.46 0.46 0.44 0.44 0.46 0.46 Polymerization solvent 372.00 372.00 378.00 378.00 372.00 372.00 Synthesis stage 2 2-isocyanatoethyl methacrylate 71.09 127.96 62.18 111.93 36.44 65.59 Reaction catalyst 0.36 0.64 0.31 0.56 0.18 0.33

[Table 2] Unit: parts by mass The first synthesis stage Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 INA 159.22 159.22 200.41 200.41 196.36 196.36 HEA - - 39.11 39.11 - - 4HBA 62.34 62.34 - 25.20 25.20 AIBN 0.44 0.44 0.48 0.48 0.44 0.44 Polymerization solvent 378.00 378.00 360.00 360.00 378.00 378.00 Synthesis stage 2 2-isocyanatoethyl methacrylate 33.54 60.37 14.24 25.63 13.56 24.40 Reaction catalyst 0.17 0.30 0.07 0.13 0.07 0.12

[table 3] Unit: parts by mass The first synthesis stage Example 13 Example 14 Example 15 IDA - 175.78 136.39 INA 173.01 - - HEA 54.54 51.76 91.16 4HBA - - - AIBN 0.46 0.46 0.46 Polymerization solvent 372.00 372.00 372.00 Synthesis stage 2 2-isocyanatoethyl methacrylate 68.51 65.02 115.73 Reaction catalyst 0.34 0.33 0.58

[Table 4] Unit: parts by mass The first synthesis stage Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 INA 213.65 213.65 204.99 204.99 109.02 109.02 94.26 94.26 HEA 39.11 39.11 - - 118.53 118.53 - - 4HBA - - 16.56 16.56 - - 127.29 127.29 AIBN 0.48 0.48 0.44 0.44 0.46 0.46 0.43 0.43 Polymerization solvent 346.76 346.76 378.00 378.00 372.00 372.00 378.01 378.01 Synthesis stage 2 2-isocyanatoethyl methacrylate 9.29 16.71 8.91 16.04 79.20 142.56 68.48 123.26 Reaction catalyst 0.05 0.08 0.04 0.08 0.40 0.71 0.34 0.62

[table 5] Unit: parts by mass Composition for adhesive layer Acrylic polymers 100 Isocyanate compound (CORONATE L) 0.75 Photopolymerization initiator (Omnirad127) 2

<Measurement of the peel strength between the adhesive layer and the adhesive layer before active energy rays (ultraviolet rays) irradiation> Cut out the part where the die-bonding layer (DAF) and the adhesive layer are attached to a size of 150 mm×20 mm. Use a hand roller to affix the die-bonding layer after removing the peeling sheet to the SUS304BA board. At this time, the SUS304BA board is placed on a hot plate heated to 80°C. When attaching, make sure that no air bubbles are mixed between the die-bonding layer and the SUS board. After that, it was placed in an environment with a temperature of 23°C and a humidity of 50% for 3 hours to fix the temperature. A Tensilon type tensile tester (manufactured by Shimadzu Corporation, AGS-J) was used to measure the peel strength (strength at which the adhesive layer was peeled off from the adhesive layer). The peeling conditions were a peeling speed of 30 mm/min, a peeling angle of 90 degrees, a temperature of 23°C, and a humidity of 50%. The measurement was performed 3 times, and the average value was used as the value of the peel strength.

＜Measurement of the peeling strength between the adhesive layer and the adhesive layer after active energy rays (ultraviolet rays) irradiation＞ In the same manner as above, after leaving it in an environment with a temperature of 23°C and a humidity of 50% for 3 hours, UV was irradiated from the substrate layer side (the back side of the film) under the following "ultraviolet radiation conditions". Furthermore, it was left in an environment with a temperature of 23° C. and a humidity of 50% for 3 hours to fix the temperature. A Tensilon type tensile tester (manufactured by Shimadzu Corporation, AGS-J) was used to measure the peel strength (strength at which the adhesive layer was peeled off from the adhesive layer). The peeling conditions were a peeling speed of 100 mm/min, a peeling angle of 90 degrees, a temperature of 23°C, and a humidity of 50%. The measurement was performed 3 times, and the average value was used as the value of the peel strength.

<Measurement of the tensile elastic modulus of the adhesive layer after ultraviolet irradiation> An adhesive layer (thickness 20 μm) was formed between a pair of PET release sheets. The adhesive layer is irradiated with ultraviolet rays under the following "ultraviolet irradiation conditions". The adhesive layer after ultraviolet irradiation was cut into a size of 10 mm×30 mm and used as an evaluation sample. Using a tensile tester (manufactured by ORIENTEC, product name "RTC-1150A"), the tensile elastic modulus of the evaluation sample was measured. Specifically, the SS curve was measured under the conditions of a measurement temperature of 22°C, a distance between the chucks of 10 mm, and a speed of 10 mm/min, and the initial elastic modulus was obtained from the rise of the SS curve. This value is taken as the tensile elastic modulus of the adhesive layer after ultraviolet irradiation. The measurement was performed 5 times, and the average value was used as the tensile elastic modulus of the adhesive layer after ultraviolet irradiation. "Ultraviolet Irradiation Conditions" Ultraviolet Irradiation Device: Product Name-UM810 (manufactured by Nitto Seiki Co., Ltd.) Light source: High-pressure mercury lamp Irradiation intensity: 50 mW/cm ² (Measuring equipment: "Ultraviolet Illuminance Meter UT-101" manufactured by Ushio Co., Ltd.) Irradiation time ：Accumulated amount of light in 6 seconds: 300 mJ/cm ²

＜Pickup test method＞ The dicing tape (ELEP MOUNT DU-300 manufactured by Nitto Denko) and the dicing ring are attached to a 12-inch bare wafer (thickness 740 μm), using a dicing saw device DFD6361 (manufactured by DISCO) to form For a groove with a depth of 100 μm and a width of 30 μm from the surface, half-cutting is performed with a size of 10 mm×10 mm. After half-cut dicing, ultraviolet rays are irradiated from the back side of the dicing tape to recover the wafer with grooves formed. After that, a back polishing tape (adhesive film for surface protection, manufactured by Nitto Denko Corporation, ELEP MOUNT UB-3083D) is attached to the surface of the wafer with grooves, and the thickness is adjusted using a polishing device DGP8760 (manufactured by DISCO). It becomes 30 μm, and a thin wafer with small pieces is obtained. The diced thin wafer and dicing ring are attached to the dicing adhesive film, ultraviolet rays are irradiated from the back side of the back polishing tape to harden the adhesive, and the back polishing tape is peeled from the wafer and removed. Secondly, using a wafer separation device DDS2300 (manufactured by DISCO), the wafer and the die bonding layer are cut and the die tape is thermally shrunk to obtain a cut sample. Specifically, first, the cold expansion unit is used to cut the semiconductor wafer under the conditions of expansion temperature: -15°C, expansion speed: 200 mm/sec, and expansion amount: 12 mm. After that, at room temperature, the expansion speed is 1 mm/sec and the expansion amount is 7 mm. Then, maintaining the expanded state, under the conditions of a heating temperature of 200°C, an air volume of 40 L/min, a heating distance of 20 mm, and a rotation speed of 5°/sec, the dicing tape on the outer periphery of the semiconductor wafer is thermally contracted. Use the wafer bonding machine SPA-300 (manufactured by Xinchuan Company) to pick up under the following conditions. The case where the pickup success rate is 90% or more at a pickup height of 400 μm or less is evaluated as 0, and the case where the pickup success rate is less than 90% is evaluated as ×. "Pickup Conditions" Number of pins: 5 Jacking speed: 1 mm/sec Pickup height: 200~1000 μm Pickup evaluation number: 50

＜Edge peeling test (between adhesive layer and adhesive layer)＞ The dicing tape (ELEP MOUNT DU-300 manufactured by Nitto Denko) and the dicing ring are attached to a 12-inch bare wafer (thickness 740 μm), using a dicing saw device DFD6361 (manufactured by DISCO) to form For a groove with a depth of 100 μm and a width of 30 μm from the surface, half-cutting is performed with a size of 12 mm×12 mm. After that, a back polishing tape (adhesive film for surface protection, ELEP MOUNT UB-3083D manufactured by Nitto Denko) was attached to the surface of the wafer with the grooves formed, and the thickness was adjusted using a polishing device DGP8760 (manufactured by DISCO). It becomes 30 μm, and a thin wafer is obtained. The diced thin wafer and dicing ring are attached to the dicing adhesive film, ultraviolet rays are irradiated from the back side of the back polishing tape to harden the adhesive, and the back polishing tape is peeled from the wafer and removed. Secondly, the wafer separation device DDS2300 (manufactured by DISCO) was used to cut the wafer and the die bonding layer and thermally shrink the dicing tape to obtain a cut sample. Specifically, first, the cold expansion unit is used to cut the semiconductor wafer under the conditions of expansion temperature: -15°C, expansion speed: 200 mm/sec, and expansion amount: 12 mm. After that, at room temperature, the expansion speed is 1 mm/sec and the expansion amount is 7 mm. Then, maintaining the expanded state, under the conditions of a heating temperature of 200°C, an air volume of 40 L/min, a heating distance of 20 mm, and a rotation speed of 5°/sec, the dicing tape on the outer periphery of the semiconductor wafer is thermally contracted. In the measurement, the amount of continuous 5 wafers (attached crystal layer [DAF]) is used, so in the measurement, the 12 wafers (with DAF) adjacent to the intended use of 5 continuous wafers (with DAF) are automatically Cut the crystal on the sticky film to remove. Then, a dicing knife was used to cut the blade into the area where the wafer (with DAF) was removed, and a 22 mm×70 mm size diced die attach film sample with 5 continuous wafers (with DAF) was obtained. Attach a double-sided tape (product No. 5000NS manufactured by Nitto Denko) on the surface of the 5 continuous wafers (the side without DAF). At this time, use a hand roller to attach the 5 continuous wafers from the end of the first wafer to the end of the fifth wafer with a width of 10 mm. Also, the double-sided tape is contained within the surface area of the wafer. That is, it is a situation in which the double-sided tape is attached without protruding from the surface of the wafer. From the state where the double-sided tape is attached to 5 continuous wafers, the release film attached to the double-sided tape is peeled off. Use a hand roller to attach the peeled surface to the SUS304BA board. After that, ultraviolet rays were irradiated from the substrate layer side of the diced chip adhesive film. The irradiation conditions are the same as those mentioned above. After UV irradiation, place the SUS board, tape, and wafer (with DAF) in an environment with a temperature of 23°C and a humidity of 50% for 3 hours. A Tensilon type tensile tester (manufactured by Shimadzu Corporation, AGS-J) was used to measure the peel strength (strength at which the adhesive layer was peeled off from the adhesive layer). The peeling conditions were a peeling speed of 50 mm/min, a peeling angle of 90 degrees, a temperature of 23°C, and a humidity of 50%. Perform 3 measurements, and use the average value of the maximum strength obtained during each measurement as the measurement value in the edge peel test.

The above evaluation results are shown in Table 6 to Table 9.

[Table 6] Structural unit of acrylic polymer Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 INA unit [mol%]: A 40 40 40 40 65 65 HEA unit [mol%] 60 60 - - 35 35 4HBA unit [mol%] - - 60 60 - - The content rate of hydroxyl-containing unit [mol%]: B (30) (6) (30) (6) (17.5) (3.5) The content rate of the unit containing polymerizable group [mol%]: C (30) (54) (30) (54) (17.5) (31.5) A/(B＋C)[Molby] 0.67 0.67 0.67 0.67 1.86 1.86 B/(B＋C)[Molby] 0.50 0.10 0.50 0.10 0.50 0.10 C/(B＋C)[Molby] 0.50 0.90 0.50 0.90 0.50 0.90 B/A[Molby] 0.75 0.15 0.75 0.15 0.27 0.05 C/A[Molby] 0.75 1.35 0.75 1.35 0.27 0.48 C/B[Molby] 1.00 9.00 1.00 9.00 1.00 9.00 ＜Properties value＞ Peel strength before UV irradiation [N/20 mm]: α 2.09 1.99 1.84 1.82 1.31 1.10 Peel strength after UV irradiation [N/20 mm]: β 0.10 0.09 0.09 0.08 0.09 0.08 Peel strength ratio (before UV irradiation/after UV irradiation) α/β 20.9 22.1 20.4 22.8 14.6 13.8 Maximum strength during edge peel test [N/10 mm] 0.47 0.49 0.32 0.37 0.15 0.17 ＜Evaluation test result＞ Pick up degree [μm] 400 400 350 350 200 200 Below 400 μm is 〇 〇 〇 〇 〇 〇 〇 Chip breakage after pick-up test No rupture No rupture No rupture No rupture No rupture No rupture When the chip is broken, it is × 〇 〇 〇 〇 〇 〇

[Table 7] Structural unit of acrylic polymer Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 INA unit [mol%]: A 65 65 85 85 85 85 HEA unit [mol%] - - 15 15 - - 4HBA unit [mol%] 35 35 - - 15 15 The content rate of hydroxyl-containing unit [mol%]: B (17.5) (3.5) (7.5) (1.5) (7.5) (1.5) The content rate of the unit containing polymerizable group [mol%]: C (17.5) (31.5) (7.5) (13.5) (7.5) (13.5) A/(B＋C)[Molby] 1.86 1.86 5.67 5.67 5.67 5.67 B/(B＋C)[Molby] 0.50 0.10 0.50 0.10 0.50 0.10 C/(B＋C)[Molby] 0.50 0.90 0.50 0.90 0.50 0.90 B/A[Molby] 0.27 0.05 0.09 0.02 0.09 0.02 C/A[Molby] 0.27 0.48 0.09 0.16 0.09 0.16 C/B[Molby] 1.00 9.00 1.00 9.00 1.00 9.00 ＜Properties value＞ Peel strength before UV irradiation [N/20 mm]: α 1.24 1.05 0.43 0.45 0.41 0.43 Peel strength after UV irradiation [N/20 mm]: β 0.08 0.07 0.10 0.09 0.09 0.08 Peel strength ratio (before UV irradiation/after UV irradiation) α/β 15.6 14.9 4.3 5.0 4.5 5.3 Maximum strength during edge peel test [N/10 mm] 0.14 0.16 0.13 0.14 0.12 0.13 ＜Evaluation test result＞ Pick up height [μm] 200 200 200 200 200 200 Below 400 μm is 〇 〇 〇 〇 〇 〇 〇 Chip breakage after pick-up test No rupture No rupture No rupture No rupture No rupture No rupture When the chip is broken, it is × 〇 〇 〇 〇 〇 〇

[Table 8] Structural unit of acrylic polymer Example 13 Example 14 Example 15 IDA unit [mol%]: A - 65 45 INA unit [mol%]: A 65 - - HEA unit [mol%] 35 35 55 4HBA unit [mol%] - - - The content rate of hydroxyl-containing unit [mol%]: B (2) (2) (3) The content rate of the unit containing polymerizable group [mol%]: C (33) (33) (52) A/(B＋C)[Molby] 1.86 1.86 0.82 B/(B＋C)[Molby] 0.06 0.06 0.05 C/(B＋C)[Molby] 0.94 0.94 0.95 B/A[Molby] 0.03 0.03 0.07 C/A[Molby] 0.51 0.51 1.16 C/B[Molby] 16.50 16.50 17.33 ＜Properties value＞ Peel strength before UV irradiation [N/20 mm]: α 1.09 1.55 3.21 Peel strength after UV irradiation [N/20 mm]: β 0.08 0.09 0.08 Peel strength ratio (before UV irradiation/after UV irradiation) α/β 13.6 17.2 40.1 Maximum strength during edge peel test [N/10 mm] 0.18 0.17 0.18 ＜Evaluation test result＞ Pick up height [μm] 200 300 200 Below 400 μm is 〇 〇 〇 〇 Chip breakage after pick-up test No rupture No rupture No rupture When the chip is broken, it is × 〇 〇 〇

[Table 9] Structural unit of acrylic polymer Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 INA unit [mol%]: A 90 90 90 90 35 35 35 35 HEA unit [mol%] 10 10 - - 65 65 - - 4HBA unit [mol%] - - 10 10 - - 65 65 The content rate of hydroxyl-containing unit [mol%]: B (5) (1) (5) (1) (32.5) (6.5) (32.5) (6.5) The content rate of the unit containing polymerizable group [mol%]: C (5) (9) (5) (9) (32.5) (58.5) (32.5) (58.5) A/(B＋C)[Molby] 9.00 9.00 9.00 9.00 0.54 0.54 0.54 0.54 B/(B＋C)[Molby] 0.50 0.10 0.50 0.10 0.50 0.10 0.50 0.10 C/(B＋C)[Molby] 0.50 0.90 0.50 0.90 0.50 0.90 0.50 0.90 B/A[Molby] 0.06 0.01 0.06 0.01 0.93 0.19 0.93 0.19 C/A[Molby] 0.06 0.10 0.06 0.10 0.93 1.67 0.93 1.67 C/B[Molby] 1.00 9.00 1.00 9.00 1.00 9.00 1.00 9.00 ＜Properties value＞ Peel strength before UV irradiation [N/20 mm]: α 0.37 0.38 0.30 0.31 2.34 2.43 2.30 2.40 Peel strength after UV irradiation [N/20 mm]: β 0.27 0.22 0.25 0.21 0.12 0.11 0.11 0.11 Peel strength ratio (before UV irradiation/after UV irradiation) α/β 1.4 1.7 1.2 1.5 19.5 22.1 20.9 21.8 Maximum strength during edge peel test [N/10 mm] 0.28 0.23 0.26 0.22 0.62 0.68 0.60 0.66 ＜Evaluation test result＞ Pick up height [μm] Can't peel off Can't peel off Can't peel off Can't peel off Can't peel off Can't peel off Can't peel off Can't peel off Below 400 μm is 〇 X X X X X X X X Chip breakage after pick-up test There is a rupture There is a rupture There is a rupture There is a rupture There is a rupture There is a rupture There is a rupture There is a rupture When the chip is broken, it is × X X X X X X X X

From the above evaluation results, it can be seen that the dicing die attach film of the example exhibits better pick-up properties than the die dicing die attach film of the comparative example. [Industrial availability]

The dicing tape and the dicing die-bonding film of the present invention are suitable for use as an auxiliary tool when manufacturing semiconductor integrated circuits, for example.

1: slicing crystal sticking film 10: Sticky crystal layer 20: Cut crystal belt 21: Substrate layer 22: Adhesive layer G: Back grinding tape H: retainer J: Adsorption fixture P: Pin member R: Slicing ring T: Tape for wafer processing U: Jack up member

Fig. 1 is a cross-sectional view of the diced die sticking film of the present embodiment cut along the thickness direction. FIG. 2A is a cross-sectional view schematically showing the half-cutting process in the manufacturing method of the semiconductor integrated circuit. FIG. 2B is a cross-sectional view schematically showing the half-cutting process in the manufacturing method of the semiconductor integrated circuit. FIG. 2C is a cross-sectional view schematically showing the half-cutting process in the manufacturing method of the semiconductor integrated circuit. FIG. 2D is a cross-sectional view schematically showing the half-cutting process in the manufacturing method of the semiconductor integrated circuit. FIG. 3A is a cross-sectional view schematically showing the state of the mounting step in the manufacturing method of the semiconductor integrated circuit. FIG. 3B is a cross-sectional view schematically showing the state of the mounting step in the manufacturing method of the semiconductor integrated circuit. 4A is a cross-sectional view schematically showing the expansion step at low temperature in the manufacturing method of the semiconductor integrated circuit. FIG. 4B is a cross-sectional view schematically showing the expansion step at a low temperature in the manufacturing method of the semiconductor integrated circuit. 4C is a cross-sectional view schematically showing the expansion step at a low temperature in the manufacturing method of the semiconductor integrated circuit. FIG. 5A is a cross-sectional view schematically showing an expansion step at room temperature in the manufacturing method of a semiconductor integrated circuit. FIG. 5B is a cross-sectional view schematically showing the expansion step at room temperature in the manufacturing method of the semiconductor integrated circuit. FIG. 6 is a cross-sectional view schematically showing the state of the pickup step in the manufacturing method of the semiconductor integrated circuit.

Claims (6)

A dicing tape is provided with a substrate layer and an adhesive layer overlapping the substrate layer, and The above-mentioned adhesive layer contains an acrylic polymer, The above-mentioned acrylic polymer contains the structural unit of C9~C11 alkyl (meth)acrylate and the structural unit of hydroxyl-containing (meth)acrylate, The acrylic polymer contains the structural units of the C9~C11 alkyl (meth)acrylate at 40 mol% or more and 85 mol% or less. The dicing tape of claim 1, wherein the acrylic polymer contains 1 mol% or more and 30 mol% or less of the structural unit of the hydroxyl-containing (meth)acrylate. Such as the dicing tape of claim 2, wherein the structural unit of the hydroxyl-containing (meth)acrylate is the structural unit of the hydroxyl-containing (meth)acrylate C2-C4 alkyl ester. The dicing tape according to any one of claims 1 to 3, wherein the acrylic polymer further has a structural unit of (meth)acrylate containing a polymerizable group. The dicing tape of claim 4, wherein the acrylic polymer is calculated in molar ratio [C/(B+C)] relative to the structural unit (B) of the hydroxyl-containing (meth)acrylate and the polymer-containing The structural unit (C) of the (meth)acrylic acid ester of a sexual group includes the structural unit (C) of the above-mentioned polymerizable group-containing (meth)acrylic acid ester of 0.50 or more and 0.95 or less. A die-cutting die-bonding film is provided with a die-cutting tape according to any one of claims 1 to 5, and a die-cutting layer laminated on the above-mentioned adhesive layer of the die-cutting tape.

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