TW201704392A - Dicing sheet, method for producing dicing sheet, and method for producing molded chip - Google Patents

Abstract

This dicing sheet is provided with a substrate and an adhesive layer that is layered on at least one surface of the substrate. The adhesive layer is formed from an adhesive composition that contains: an acrylic polymer (A) having an energy ray-polymerizable group and a reactive functional group; and an isocyanate crosslinking agent (B) capable of a crosslinking reaction with the reactive functional group. The storage elastic modulus of the adhesive layer at 23 DEG C is 50-80 kPa prior to irradiation with energy rays and 5.0 MPa or more after irradiation with energy rays. The thickness of the adhesive layer is less than 20 [mu]m. The energy amount of the surface of the adhesive layer as measured using probe tack prior to irradiation with energy rays under a condition in which the peeling speed is changed by 1 mm/minute in accordance with the method described in JIS Z0237:1991 is 0.1-0.8 mJ/5 mm[Psi]. This dicing sheet reduces the possibility of the occurrence of defects in any of a dicing step, an expansion step, and a pick-up step. The use of this dicing sheet makes it possible to produce a cost-effective molded chip of excellent quality.

Description

Cutting sheet, manufacturing method of the same, and method of manufacturing the same

The present invention relates to a dicing sheet, a method of manufacturing the dicing sheet, and a method of manufacturing a mold wafer. The dicing sheet according to the present invention is, in particular, a dicing sheet used for dicing a mold assembly such as a semiconductor component in which a plurality of wafer-shaped components such as a semiconductor wafer are encapsulated by a resin. Further, the present invention relates to a method for producing the above-mentioned dicing sheet, and a method for producing a mold wafer using the dicing sheet manufacturing method and the dicing sheet.

In the case where a wafer-shaped component such as a semiconductor wafer is packaged in a resin (referred to as a "mold wafer" in the specification of the present invention), and a packaged wafer-shaped component is a semiconductor wafer, it is usually produced as follows.

First, a semiconductor wafer is loaded on each of the agglomerates of agglomerates continuously formed by a plurality of submounts, such as TAB tape automated bonding, and the semiconductor wafers are all resin-packed together to obtain an electronic component agglomerate (the present invention) The patent specification is called "semiconductor component").

Next, the semiconductor component is fixed to the dicing sheet by adhering a bonding sheet having a substrate and an adhesive layer (referred to as "cutting sheet" in the patent specification) on one surface of the semiconductor component. The semiconductor component fixed to the dicing sheet is cut (separated) and then sliced, and a plurality of members adjacent to the mold wafer are formed on the dicing sheet (cutting process).

Typically, the adhesive layer of the dicing sheet is designed to reduce the adhesion of the adhesive layer to the bonded surface by a specific stimulus. For this particular stimuli, for example, energy lines may be employed. The irradiation also includes a process of irradiating the dicing sheet with an energy ray to make the adhesion to the adhesive layer of the bonded surface low before performing the following processes.

Then, according to the need, the cutting piece of the member is expanded (expanding in the direction of the main surface), and the distance between the mold wafers arranged on the cutting piece is widened (extension process).

The mold wafers in a state in which they are separated from each other on the dicing sheet are individually picked up, separated from the dicing sheet (pushing process), and then transferred to the next process. At this time, it is easier to perform the topping because it includes a process for reducing the adhesion of the adhesive layer to the die surface of the mold.

In a series of processes in the cutting process, the semiconductor component and its cut die wafer are maintained in a fixed state on the dicing sheet. From the viewpoint of achieving the purpose, the adhesive layer of the dicing sheet is for the semiconductor component. The surface of the mold and the surface of the mold wafer before the irradiation of the energy line are preferably high.

In the case of the dicing die semiconductor system of the dicing sheet, the surface to be bonded is generally the surface of the sealing resin, and the unevenness of the surface to be bonded tends to be larger than when the semiconductor wafer is used as the adhering body. Therefore, in the above process of transferring a semiconductor wafer as a dicing sheet of an adherend to a semiconductor device, the above-mentioned adhesiveness to the bonded surface becomes insufficient, resulting in a cutting process. In the step of cutting the semiconductor component, the mold wafer formed by the singulation of the semiconductor component is peeled off from the dicing sheet. Produced in the following cutting process This defect is called "wafer flying".

In order to reduce the possibility of occurrence of scattering of the wafer, for example, as described in Patent Document 1, the adhesive layer of the dicing sheet contains a resin for improving the adhesion to the bonded surface in the state before the irradiation of the energy ray. Material (referred to as "bonding resin" in the patent specification of the present invention).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-229040

In the adhesion-imparting resin, a general rosin-based material is an ideal material from the viewpoint of adhesion to the bonded surface of the adhesion-promoting layer. However, the inventors have found in detail that in the case where the adhesive layer contains a material having a lower molecular weight than the resin imparted to the resin, the topping process cannot be properly performed, specifically, the topping takes place. The problem that the mold wafer cannot be taken up during the process. In the following, the problems that occur in the topping process are collectively referred to as "top failure."

In addition, in the cutting process, it is sometimes necessary to reduce the possibility of the so-called "residual glue" adhered to the mold wafer formed by the die-cutting of the mold component, and the substance formed by the adhesive layer of the dicing sheet adheres. When the residual glue is generated, the handleability of the mold wafer in the cutting process and the subsequent process is lowered, and the residual glue is regarded as one of the problems in the cutting process in the patent specification of the present invention.

The present invention has been made in view of the above problems, and aims to provide A cutting piece and a manufacturing method thereof for reducing the possibility of occurrence of any process (specifically, such as wafer scattering, residual glue, and poor ejection) in a cutting process and a pick-up process, and a mold wafer using the same Production method.

In order to achieve the above object, the present invention provides the following contents.

(1) A dicing sheet comprising a layer of an adhesive layer provided on at least one surface of the substrate and the substrate, wherein the adhesive layer is composed of an energy ray-polymerizable group and a reactive functional group. The acrylic polymer (A), and the reactive functional group are formed with an adhesive composition of the isocyanate-based bridging agent (B) which is capable of bridging reaction; the above acrylic polymer (A) has the above reactive functional group The acrylic polymer (A1) and the isocyanate compound (A2) having the above energy ray-polymerizable group are obtained by reacting in the presence of an organometallic catalyst (C) containing at least one of titanium and zirconium. The storage modulus of the adhesive layer at a temperature of 23 ° C is 50 kPa or more and 80 kPa or less in a state before the irradiation of the energy ray, and is 5.0 MPa or more in a state after the irradiation of the energy ray. The thickness of the adhesive layer is less than 20 μm, and the surface of the adhesive layer is in a state before the irradiation of the energy ray, and in the method described in JIS Z0237: 1991, the peeling speed is changed to 1 mm/min. The amount of energy measured by the probe type tacker is 0.1 mJ/5 mm ψ or more and 0.8 mJ/5 mm ψ or less.

(2) The dicing sheet according to the above (1), wherein the storage modulus of the adhesive layer at 23 ° C is 500 MPa or less in a state after the irradiation of the energy ray.

(3) The dicing sheet according to the above (1) or (2), wherein the acrylic polymer (A1) is provided for providing a monomer (m1) having a constituent unit of the reactive functional group. Monomer of the above acrylic polymer (A1), quality In the reaction for forming the acrylic polymer (A), the amount of the compound (A2) used is 0.4 equivalent or more and 0.9 equivalent or less to the monomer (m1). .

(4) The dicing sheet according to any one of (1) to (3), wherein the organic metal catalyst (C) comprises a zirconium tong compound.

(5) The dicing sheet according to any one of (1) to (4), wherein, in use, a semiconductor component obtained by resin-sealing a semiconductor wafer is adhered to a reverse surface of the substrate surface of the adhesive layer The resin package surface.

(6) A method of producing a dicing sheet comprising a substrate and a dicing sheet of an adhesive layer laminated on at least one side of the substrate, comprising: an energy ray-polymerizable group And an acrylic polymer (A) having a reactive functional group and an adhesive composition of an isocyanate-based bridging agent (B) capable of bridging the reactive functional group on one side of the substrate, obtained Forming the adhesive layer on the coating film to obtain the dicing sheet; and applying the adhesive composition to the peeling surface of the release sheet to form the adhesive layer on the obtained coating film, The surface of the adhesive layer on the release sheet that is opposite to the surface of the release sheet is adhered to one surface of the substrate, and the dicing sheet is attached to the adhesive layer and adhered to the release sheet. At least one process in the process. The acrylic polymer (A) is an acrylic polymer (A1) having the above reactive functional group, and an isocyanate compound (A2) having the above energy ray polymerizable group, and contains at least one of titanium and zirconium. The reaction is obtained in the presence of an organometallic catalyst (C). Providing the above-mentioned acrylic polymer (A1) for the monomer (m1) which provides the constituent unit having the above-mentioned reactive functional group in the above acrylic polymer (A1) The mass ratio of the entire monomer is 5% by mass or more and 30% by mass or less. In the reaction for forming the acrylic polymer (A), the amount of the compound (A2) used is 0.4 for the monomer (m1). The amount of the adhesive layer is less than 20 μm, and the storage modulus of the adhesive layer at 23° C. is 50 kPa or more and 80 kPa or less in the state before the irradiation of the energy ray. In the state after the line, the surface of the adhesive layer is 5.0 MPa or more, and in the state described in JIS Z0237:1991, the peeling speed is changed to 1 mm/min. The amount of energy measured using a probe-type initial tack tester is 0.1 mJ/5 mm ψ or more and 0.8 mJ/5 mm ψ or less.

(7) The layer of the adhesive in the dicing sheet according to any one of the above (1) to (5) is adhered to the resin package surface of the mold assembly, and the mold assembly on the dicing sheet is cut to be A method of manufacturing a mold wafer in which a plurality of mold wafers are obtained.

The present invention provides a cutting piece and a manufacturing method thereof that can reduce the possibility of occurrence of a problem regardless of any of the cutting process, the stretching process, and the topping process. Further, by using such a dicing sheet, a mold wafer excellent in quality and cost-effective can be manufactured.

Hereinafter, embodiments of the present invention will be described.

Cutting piece

A dicing sheet according to an embodiment of the present invention has a substrate and an adhesive layer.

(1) Substrate

The base material of the dicing sheet according to the present embodiment is not particularly limited as long as it is not broken during the topping process, and is usually formed of a film using a resin material as a main material. Specific examples of the film may be exemplified by a polyethylene film such as a low density polyethylene (LDPE) film, a linear low density polyethylene (LLDPE) film, or a high density polyethylene (HDPE) film; a polypropylene film, a polybutylene film, and a poly film. a polyolefin film such as a butadiene film, a polymethylpentene film, an ethylene-norbornene copolymer film or a norbornene resin film; a polyvinyl chloride film such as a polyvinyl chloride film or a vinyl chloride copolymer film; a polyester film such as an ethylene phthalate film or a polyethylene terephthalate film; a polyurethane film; a polyimine film; an ionic polymer resin film; an ethylene-vinyl acetate film; An ethylene-based polymer film such as an ethylene-(meth)acrylic acid copolymer film or an ethylene-(meth)acrylate copolymer film; a polystyrene film, a polycarbonate film; a fluororesin film; and a hydride of the foregoing resin A film or the like which is modified as a main material. Further, the above-mentioned bridge film or copolymer film can also be used. The substrate may be used alone or in combination of two or more. Further, "(meth)acrylic acid" in the specification of the present invention means acrylic acid and methacrylic acid, and the same applies to other similar terms.

As the substrate, various additives such as a coloring agent, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler may be added to the film made of the above-mentioned resin material as a main material. As the coloring agent, a pigment such as titanium oxide or carbon black or a plurality of different pigments can be exemplified, and in addition, as the filler, for example, An organic material of the same nature as a melamine resin, an inorganic material of the same nature as that of a gas phase ceria, and a metal material of the same nature as a nickel particle. Although the content of such an additive is not particularly limited, the substrate needs to be fixed in such a range that it can exert a desired function without losing the required smoothness and ductility.

In the case of using an ultraviolet ray, the substrate is highly transparent to ultraviolet rays in the case of using an ultraviolet ray, and in the case of using an electron beam, in the case of an energy beam, The substrate is preferably penetrating for the electron beam.

In the respective processes described above, the thickness of the substrate is not limited as long as it can function properly, and is preferably in the range of 20 to 450 μm, more preferably 25 to 200 μm, and particularly preferably 50 to 150 μm. .

In the present embodiment, when the breaking elongation of the substrate is 23 ° C and the relative humidity is 50%, the measured value is preferably 100% or more, more preferably 200% or more and 1000% or less. It is difficult to break the substrate of the above-mentioned breaking extension system by 100% or more even if the stretching process is performed, and the mold wafer formed by cutting the mold assembly becomes easier to be separated. In addition, the elongation extends in the extension test extension test based on JIS K7161:1994, which is the elongation of the test piece length for the original length when the test piece is damaged.

Further, in the present embodiment, the substrate is subjected to a test based on JIS K7161:1994, and the tensile stress measured at 25% of the deformation is preferably 5 N/10 mm or more and 15 N/10 mm or less, and the maximum tensile stress is 15 MPa or more and 50 MPa. The following is better. In the case of 25% modification, if the tensile stress is less than 5 N/10 mm or the maximum tensile stress is less than 15 MPa, when the dicing sheet is bonded to the mold frame and fixed to the annular frame, slack occurs due to the softness of the substrate, thus causing a shift error. The reason. another On the other hand, in the case of 25% modification, if the tensile stress exceeds 15 N/10 mm or the maximum tensile stress exceeds 50 MPa, in the case where the stretching process is performed, since the load applied to the dicing sheet becomes large, the dicing sheet is peeled off from the annular frame. After the problem occurs. In the 25% variation of the breaking extension of the present invention, the tensile stress and the maximum tensile stress mean values measured for the length direction of the substrate.

(2) adhesive layer

The adhesive layer of the dicing sheet according to the present embodiment is exemplified by an acrylic polymer having an energy ray-polymerizable group and a reactive functional group having a thickness of less than 20 μm and having a predetermined characteristic such as a storage modulus. (A), and an adhesive composition of an isocyanate-based bridging agent (B) which is reactively bridged with a reactive functional group.

(2-1) Thickness

The thickness of the adhesive layer of the dicing sheet according to the embodiment is less than 20 μm, and if the thickness of the adhesive layer is less than 20 μm, the residual glue is less likely to be generated, and the possibility of occurrence of a problem in the cutting process can be reduced. It also reduces the possibility of problems in the topping process. In particular, when the dicing process is performed, the mold assembly is diced into a mold wafer, and the time until the energy ray irradiation is performed is long (for example, 30 days), and the thickness of the adhesive layer is 20 μm or more for the mold. The adhesion of the adhesive layer on the wafer surface will become too high, and even if the energy ray is irradiated, the above-mentioned adhesiveness cannot be appropriately lowered, and the possibility of occurrence of the erroneous removal is improved. Since the thickness of the adhesive layer of the dicing sheet according to the present embodiment is less than 20 μm, the possibility of occurrence of a problem in the pick-up process can be stably reduced. The thickness of the adhesive layer having the dicing sheet according to the present embodiment is preferably 17 μm or less, more preferably 13 μm or less, and particularly preferably 10 μm or less. Stable bonding The thickness of the adhesive layer is preferably 2 μm or more, more preferably 4 μm or more, and particularly preferably 5 μm from the viewpoint of having an appropriate adhesion to the bonded surface. Therefore, the optimum thickness of the adhesive layer is 5 μm or more and 10 μm or less.

(2-2) Storage modulus

The storage modulus at 23 ° C of the adhesive layer before the energy ray of the dicing sheet of the dicing sheet according to the embodiment is also referred to as "the elastic modulus before irradiation" in the patent specification of the present invention. 50 kPa or more and 80 kPa or less.

The adhesive layer forming material before the energy ray irradiation becomes inaccessible in the depressed portion of the surface of the encapsulating resin of the mold assembly of the adhesive layer by the elastic modulus before the irradiation. Bad topping is not easy to happen. Further, since the modulus of elasticity before the irradiation is in the above range, the adhesion to the adhered surface of the adhesive layer becomes appropriate, and the scattering of the wafer does not easily occur. The elastic modulus before irradiation is preferably 50 kPa or more and 75 kPa or less, more preferably 50 kPa or more and 70 kPa or less from the viewpoint of stably reducing the possibility of occurrence of chipping failure and wafer scattering.

The adhesive layer of the dicing sheet according to the present embodiment, the storage modulus of the adhesive layer after the irradiation of the energy ray at 23 ° C (also referred to as "the elastic modulus after irradiation" in the patent specification of the present invention" ) is 5.0 MPa or more.

After the irradiation, since the elastic modulus is 5.0 MPa or more, the material of the adhesive layer which is irradiated with the energy ray in the depressed portion of the surface of the encapsulating resin of the mold component of the adhesive layer of the adhesive layer becomes difficult to enter. It is difficult to take bad things. From the viewpoint of stably reducing the possibility of occurrence of the occurrence of the topping failure, the elastic modulus after the irradiation is preferably 10 MPa or more, more preferably 15 MPa or more, and particularly preferably 20 MPa or more.

In the depressed portion of the surface of the encapsulating resin of the mold assembly of the adhesive layer of the adhesive layer, the adhesive layer forming material that enters is appropriately detached from the recessed portion in the topping process, even if the above The elastic modulus after the irradiation is preferably 800 MPa or less, more preferably 700 MPa or less, more preferably 500 MPa or less, and particularly preferably 200 MPa or less from the viewpoint of occurrence of breakage in the depressed portion and difficulty in preventing the topping.

(2-3) TACK value

In the method described in JIS Z0237:1991, the surface of the adhesive layer of the dicing sheet according to the present embodiment is changed to a condition of 1 mm/min in the method described in JIS Z0237:1991, and the probe type is used. The amount of energy measured by the Probe tack (also referred to as "TACK value" in the patent specification of the present invention) is 0.1 mJ/5 mm ψ or more and 0.8 mJ/5 mm ψ or less. This TACK value is obtained as the measured peak integrated value from the start of the measurement to the probe peeling, and the occurrence of wafer scattering can be suppressed by the TACK value being in the above range. From the viewpoint of more stably reducing the possibility of wafer scattering, the TACK value is preferably 0.13 mJ/5 mm ψ or more and 0.75 mJ/5 mm ψ or less, preferably 0.15 mJ/5 mm ψ or more, 0.7 mJ/5 mm. ψ The following is more preferably 0.18 mJ/5 mm ψ or more and 0.65 mJ/5 mm ψ or less.

(2-4) Acrylic polymer (A)

The adhesive composition for forming the adhesive layer having the dicing sheet according to the present embodiment contains an acrylic polymer (A) having an energy ray polymerizable group and a reactive functional group. The acrylic polymer (A) is an acrylic polymer contained in a unit constituting the structure of the acrylic compound having an energy ray polymerizable group and a reactive functional group. Acrylic polymerization The compound (A) may be a homopolymer polymer obtained by polymerizing one type of monomer, or may be a copolymer obtained by polymerizing a plurality of monomers. The acrylic polymer (A) copolymer is preferred from the viewpoint of easily suppressing physical properties and chemical properties of the polymer.

The polystyrene-equivalent weight average molecular weight (Mw) of the acrylic polymer (A) is preferably 10,000 to 2,000,000, and the acrylic polymer (A) is a maintenance function which exhibits a general function as a binder main agent. The effect of the adhesiveness of the adhesive layer, which is more pronounced when the molecular weight is larger. On the other hand, if the molecular weight of the acrylic polymer (A) is too large, it is difficult to form a thin layer when the adhesive layer is produced. Therefore, the polystyrene-equivalent weight average molecular weight (Mw) of the acrylic polymer (A) is preferably from 100,000 to 1,500,000. Further, the glass transition temperature Tg of the acrylic polymer (A) is preferably from -70 to 30 ° C, more preferably from -60 to 20 ° C. Further, the polystyrene-equivalent weight average molecular weight of the present specification is a polystyrene-converted value measured by gel permeation chromatography (GPC).

The reactive functional group of the acrylic polymer (A) is a functional group which can be bridge-reacted with the isocyanate-based bridging agent (B) which will be described later, and examples thereof include a hydroxyl group, a carboxyl group, an amine group and the like. Among them, a hydroxyl group having high reactivity with an isocyanate group of the isocyanate-based bridging agent (B) is preferred as a reactive functional group of the acrylic polymer (A).

The type of the energy ray polymerizable group of the acrylic polymer (A) is not particularly limited, and specific examples thereof include a functional group having an ethylenically unsaturated bond such as a vinyl group or a (meth) acryl group. From the viewpoint of excellent polymerization reactivity, the energy ray polymerizable group is preferably a functional group having an ethylenically unsaturated bond, and (meth) propylene oxime from the viewpoint of high reactivity at the time of irradiation of the energy ray. The base is better.

As for the energy line for reacting the energy ray polymerizable group, Here are a few examples of free radiation, namely X-rays, ultraviolet rays, electron beams, and the like. Among them, ultraviolet rays which are easy to introduce by irradiation equipment are preferred.

In the case of utilizing ultraviolet rays, in the case of utilizing ultraviolet rays, it is preferable to use near-ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm from the viewpoint of handling convenience. The amount of the ultraviolet ray is appropriately set according to the type of the energy ray polymerizable group of the acrylic polymer (A) and the thickness of the adhesive layer, and is usually about 50 to 500 mJ/cm ² , preferably. lines 100 ~ 450mJ / cm ^2, more preferably based 150 ~ 400mJ / cm ^2. Further, an ultraviolet line illumination generally 50 ~ 500mW / cm ² or so, preferably based 100 ~ 450mW / cm ^2, more preferably based 150 ~ 400mW / cm ^2. The ultraviolet source is not particularly limited, and for example, a high pressure mercury lamp, a metal halide lamp, or the like can be used.

In the case of using the electron beam, the acceleration radiation can be appropriately set according to the type of the energy ray polymerizable group having the acrylic polymer (A) and the thickness of the adhesive layer. Yes, usually the acceleration voltage is about 10~1000kV. Further, the amount of the irradiation line is preferably set within a range in which the reaction of the energy ray polymerizable group having the acrylic polymer (A) is appropriately carried out, and is usually set in the range of 10 to 1000 krad. There is no particular limitation on the electron beam source, for example, a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, a core insulating transformer type, Or various types of electron beam accelerators such as linear type, high frequency high voltage type (Dynamitron), and high frequency type.

The acrylic polymer (A) is composed of an acrylic polymer (A1) having a reactive functional group and an isocyanate compound (A2) having an energy ray-polymerizable group, and at least one of titanium and zirconium The presence of the media (C) Obtained by the next reaction. The resulting adhesive composition containing the acrylic polymer (A) can be formed into a paste having an appropriate pre-irradiation modulus and an appropriate TACK value by reaction in the presence of an organic metal catalyst (C). Agent layer.

(2-4-1) Acrylic Polymer (A1)

The acrylic polymer (A1) has the reactive functional acrylic polymer described above, and provides a reactive functional group constituent unit of the acrylic polymer (A1) (m1) for providing acrylic polymerization. The mass of the monomer of the substance (A1) is preferably 5% by mass or more and 30% by mass or less. By satisfying the above-mentioned specifications of the mass ratio, the acrylic polymer-containing (A) adhesive composition obtained from the acrylic polymer (A1) can be formed to have an appropriate pre-irradiation modulus and an appropriate TACK value. Adhesive layer. The mass ratio is preferably 7% by mass or more and 25% by mass or less, more preferably 10% by mass or more and 20% by mass or less, and particularly preferably 12% by mass or more and 17% by mass or less.

When the acrylic polymer (A1) is a reactive functional group and a hydroxyl group is used, a monomer which can be used for forming the acrylic polymer (A1) can be specifically exemplified.

As a monomer which is used for forming a raw material of the acrylic polymer (A1) having a hydroxyl group (also referred to as "raw material monomer" in the specification of the present invention), an acrylic monomer having a hydroxyl group can be exemplified. Also referred to in the patent specification of the invention is a "hydroxy acrylic monomer", a non-acrylic monomer having a hydroxyl group, an acrylic monomer having no hydroxyl group, and a non-acrylic monomer having no hydroxyl group. The hydroxyl group-containing acrylic polymer (A1) contains, in the raw material monomer, a constituent unit derived from at least one selected from the group consisting of a hydroxyl group-containing monomer and a hydroxyl group-free acrylic monomer, so that the polymer becomes Acrylic polymer, At the same time, a constituent unit derived from at least one of a hydroxyl group-containing monomer and a hydroxyl group-containing non-acrylic monomer is contained so that the polymer (A1) has a hydroxyl group.

Specific examples of the hydroxy acrylic monomer include a hydroxyl group (meth) acrylate, 2-hydroxypropyl (meth) acrylamide, N-methylol acrylamide, etc. (methyl group) )Acrylate. Further, as a specific example of the non-acrylic monomer having a hydroxyl group, there is a vinyl hydroxyacetate or the like. The acrylic polymer having a hydroxyl group contains a constituent unit derived from a hydroxy acrylic monomer, and the monomer having a hydroxyl group as described above is preferable from the viewpoint of high handleability and ease of physical properties of the adhesive layer. From the viewpoint of easily controlling the amount of the energy ray polymerizable group in the acrylic polymer (A), a monomer having only one hydroxyl group is preferred.

Among the above raw material monomers, specific examples of the acrylic monomer having no hydroxyl group are (meth)acrylic acid, (meth)acrylic acid ester, and derivatives thereof (acrylonitrile or the like). More specific examples of (meth) acrylate are methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (methyl) (meth) acrylate having a chain structure such as acrylic acid; cycloalkyl (meth) acrylate, diphenylethylenedione (meth) acrylate, isodecyl (meth) acrylate, dicyclopentane Base (meth) acrylate, dicyclopentenyl (meth) acrylate, bicyclodecane (meth) acrylate, tetrahydroindenyl (meth) acrylate, imide acrylate, etc. (meth)acrylate having a structure such as a (meth) acrylate; a reactive functional group (meth) acrylate other than a hydroxyl group such as glycidyl methacrylate or N-methylaminoethyl (meth) acrylate. Further, in the case of an acrylic mono-system alkyl (meth) acrylate having no hydroxyl group, the alkyl group has a carbon number of from 1 to 18 The range is better. Further, examples of the non-acrylic monomer having no hydroxyl group include olefins such as ethylene and norbornene, vinyl acetate, and styrene.

(2-4-2) Isocyanate Compound (A2)

The isocyanate compound (A2) has an energy ray polymerizable group and a compound which may have an isocyanate group when reacted with a reactive functional group contained in the acrylic polymer (A1). Examples of such an isocyanate compound include a compound having an isocyanate group, a compound having a blocked isocyanate group, a biuret or a trimeric isocyanate having a compound having an isocyanate group, and having a different A compound of a cyanate group, and a modified substance such as an ethylene glycol, trimethylolpropane or castor oil and a reactant addition object containing a non-aromatic low molecular weight active hydrogen compound.

Specific examples of the isocyanate compound (A2) include (meth)methacryloyloxyethyl isocyanate, and a reaction product of at least one hydroxyl group-containing (meth) acrylate and polyisocyanate compound is also It can be mentioned as a specific example of the isocyanate compound (A2). Among them, from the viewpoint of facilitating the control of the amount of the energy ray polymerizable group in the acrylic polymer (A), an isocyanate compound having only one energy ray polymerizable group is preferred, and more preferably (methyl group) ) methacryloyloxyethyl isocyanate.

In the reaction for forming the acrylic polymer (A), the amount of the compound (A2) to be used is preferably 0.4 equivalent or more and 0.9 equivalent or less to the monomer (m1) related to the acrylic polymer (A). The adhesive composition of the acrylic polymer (A) obtained from the acrylic polymer (A1) and the compound (A2) by the above-mentioned specification of the amount of the compound (A2) used, and the adhesive obtained thereby It is possible to prevent the layer from becoming too hard after the irradiation of the energy ray, or to reduce the adhesion to the surface to be bonded due to the irradiation of the energy ray, and thus it may be insufficient. As a result, cutting can be achieved Chip topping on the chip becomes easy. The amount of the compound (A2) to be used in the monomer (m1) is preferably 0.4 equivalent or more and 0.8 equivalent or less, more preferably 0.45 equivalent or more and 0.75 equivalent or less, and particularly preferably 0.5 equivalent or more and 0.7 equivalent or less.

(2-5) Isocyanate bridging agent (B)

The "isocyanate bridging agent" in the specification of the present invention is a polyisocyanate compound, and means a general term for bridging property, and specific examples thereof include aromatics such as toluene isocyanate, diphenylmethane diisocyanate, and phenyl diisocyanate. An alicyclic isocyanate compound such as polyisocyanate; cyclohexylamine-4, 4'-diisocyanate, bicyclotriisocyanate, cyclopentylene diisocyanate, cyclohexane diisocyanate, methylcyclohexyl diisocyanate, hydrogenated phenyl diisocyanate; Acyclic aliphatic isocyanate such as hexamethylene diisocyanate, trimethylcyclohexane diisocyanate or lysine diisocyanate, and a compound thereof having a biuret or isocyanurate body and an isocyanate group And modified substances such as ethylene glycol, trimethylolpropane, castor oil and other non-aromatic low molecular weight active hydrogen-containing compounds and reactant addition objects. In the adhesive composition, one or more compounds are preferable as the isocyanate bridging agent (B).

The content of the isocyanate-based bridging agent (B) in the adhesive composition is not limited, and can be appropriately set depending on the type of the isocyanate-based bridging agent (B). In a non-limiting example, the total amount of the adhesive composition is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 7% by mass or less, and particularly preferably 0.1% by mass or more and 3% by mass or less. .

(2-6) Organometallic catalyst (C)

The organometallic catalyst (C) contains at least one of titanium and zirconium. Specifically, it is formed of an organometallic compound containing at least one of titanium and zirconium. The organometallic compound may, for example, be a metal oxide, a condensate or an acylate, and specific examples thereof include a titanium alkoxide, a titanium tong, a zirconium azide, a zirconium tong, and the like. Among them, the metal element contained in the organometallic compound preferably contains zirconium, and the metal element is preferably zirconium. Further, the organometallic compound is preferably a compound of a chelating compound. Therefore, the organometallic catalyst (C) preferably contains a zirconium tong compound, and more preferably a compound having a zirconium chelating compound.

The organometallic catalyst (C) does not contain a tin organometallic compound, although the cause is not clear, but if the binder composition organometallic catalyst (C) does not contain a tin organometallic compound, it can be easily An adhesive layer having an appropriate pre-irradiation modulus of elasticity and an appropriate TACK value is formed.

In order to obtain the reaction of the acrylic polymer (A), the amount of the organometallic catalyst (C) to be used is not limited. When the amount of use of the acrylic polymer (A1) is 100 parts by mass, the amount is preferably 0.01 parts by mass or more and 0.5 parts by mass or less, more preferably 0.01 parts by mass or more and 0.3 parts by mass or less, more preferably 0.01% by mass. More than 0.25 parts by mass or less.

(2-7) Other ingredients

The adhesive composition for forming the adhesive layer having the dicing sheet according to the embodiment may be a coloring material such as a photoinitiator (D), a tackifying resin, a dye, or a pigment, and the like. Various additives such as flame retardants, fillers, and antistatic agents.

Here, the photoinitiator (D) will be described in detail. Examples of the photoinitiator (D) include a benzoin compound, a methylphenylketone compound, an acylphosphine oxide compound, a dichlorotitanium compound, and a thiophene compound. a photoinitiator such as a ketone compound or a peroxy compound, a photo-sensitive agent such as an amine or a hydrazine, etc., and specifically, a 1-hydroxycyclohexane Phenyl ketone, benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, diphenylethylenedione thioether, tetramethylamine thioformamidine, azobisisobutyronitrile, bibenzyl, hydrazine , β-fluorene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. In the case of the energy ray, when the ultraviolet ray is used, the irradiation time and the irradiation amount can be reduced by using the photoinitiator (D).

(2-8) Method for producing adhesive composition

The method of producing the adhesive composition for forming the adhesive layer is not limited. It is preferred to manufacture according to the method described below.

First, as a one-step process, an acrylic polymer (A1) and an isocyanate compound (A2) are reacted in the presence of an organic metal catalyst (C) to obtain an acrylic polymer (A) and an organic metal contact. The product of the component based on the medium (C) may be a solvent as appropriate in the above reaction. The reaction conditions of the reaction in the first process are appropriately set depending on the type and content of the acrylic polymer (A1), the isocyanate compound (A2), and the organometallic catalyst (C) of the reaction raw material. By such a reaction, a product containing an acrylic polymer (A) and a component based on the organic metal catalyst (C) can be obtained. The component based on the organometallic catalyst (C) preferably maintains the catalytic activity. By maintaining the catalytic activity, the reaction catalyst of the acrylic polymer (A) and the isocyanate bridging agent (B) which are formed when the adhesive layer is formed in the adhesive composition can exhibit an organic metal catalyst. (C) is the component function of the benchmark.

In the second process which is carried out after the first process, a product containing the first process, an isocyanate-based bridging agent (B), and a mixture of the photoinitiator (D) and the like as required are used as the binder composition. And get. The product of the first process may include a solvent removal step or the like as long as it contains the acrylic polymer (A). There is no limitation on the method of mixing, and the uniformity of the mixture is increased as much as possible, and the setting can be appropriately set.

(3) peeling sheet

The dicing sheet according to the embodiment is applied to the mold component of the adhesive body (specifically, the semiconductor component is specifically exemplified), and the substrate for the adhesive layer is used for the purpose of protecting the adhesive layer. The peeling surface of the peeling sheet is bonded to the opposite surface of the opposing surface. The composition of the release sheet can be arbitrarily adjusted, and for example, a release agent can be applied to the plastic film. As a specific example of the plastic film, a polyester film such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate can be exemplified, and in the case of a release agent, Polyfluorenes, fluorines, long-chain alkyls, and the like can be used, but polyoxanes which are inexpensive and which have stable properties can be preferably used. The plastic film of the release sheet may be replaced by a paper substrate such as cellophane, coated paper or Daolin paper, or a laminated paper of a thermoplastic resin such as polyethylene laminated on a paper substrate. The thickness of the release sheet is not particularly limited, and is usually about 20 μm or more and 250 μm or less.

2. Manufacturing method of cutting piece

The method for producing the dicing sheet is not particularly limited as long as the adhesive layer formed of the above-described adhesive composition can be laminated on one surface of the substrate. For example, after the adhesive composition described above and the solvent-containing coating liquid added according to the required addition, a mold coater, a curtain coater, a spray coater are used on one side of the substrate. A coating solution such as a slit coater or a knife coater can form an adhesive layer by drying the coating film on the surface of the single side. The coating liquid is not particularly limited, and may be contained as a solute for forming a component of the adhesive layer, or may be contained as a dispersion.

By adjusting the above drying conditions (temperature, time, etc.), in addition, another The bridging treatment is used to bridge the acrylic polymer (A) and the isocyanate bridging agent (B) in the coating film to form a desired bridging structure having a density in the adhesive layer. In order to sufficiently carry out the bridging reaction, after the adhesive layer is laminated on the substrate by the above method or the like, the obtained cut sheet is usually subjected to a standing rest for several days, for example, in an environment of 23 ° C and a relative humidity of 50%. .

Or coating a coating liquid on the release surface of the release sheet to form a coating film, and drying it to form a laminate made of an adhesive layer and a release sheet, or in the adhesive layer of the laminate The opposite side of the opposite surface of the release sheet is adhered to one side of the substrate to obtain a laminate of the dicing sheet and the release sheet. The release sheet of the laminate may be peeled off as a process material or may be peeled off before being adhered to the mold assembly to protect the adhesive layer.

As described above, the manufacturing method according to an embodiment of the present invention has one of the following processes: applying an adhesive composition containing an acrylic polymer (A) and an isocyanate bridging agent (B) to a substrate. One side of the material forms an adhesive layer on the obtained coating film to obtain a process of the above-mentioned dicing sheet; and the adhesive composition is applied to the peeling surface of the release sheet, and the adhesive film layer is formed through the obtained coating film. The surface of the adhesive layer on the release sheet opposite to the surface opposite to the release sheet is adhered to one surface of the substrate to obtain a dicing sheet in a state in which the release sheet is adhered to the surface on the adhesive layer side.

Here, as described above, the acrylic polymer (A) is obtained by reacting an acrylic polymer (A1) and an isocyanate compound (A2) in the presence of an organic metal catalyst (C), for an acrylic polymer. The mass ratio of the entire monomer supplied by the acrylic polymer (A1) of the monomer (m1) in (A1) is preferably 5% by mass or more and 30% by mass or less, and is used for forming an acrylic polymer (A). Reaction The amount of the compound (A2) to be used is preferably 0.4 equivalent or more and 0.9 equivalent or less to the monomer (m1).

3. Method for manufacturing mold wafer

The method of manufacturing a mold wafer from a mold assembly by the dicing sheet according to the present embodiment, and the case where the mold unit is formed of a semiconductor element, will be specifically described below as an example.

The semiconductor component is a semiconductor wafer loaded on each of the agglomerates of the agglomerates as described above, and the electronic component agglomerates in which the semiconductor wafers are encapsulated together by a resin, usually having a base surface resin encapsulation surface, the thickness of which is 200 to 2000 μm. about. The resin sealing surface is treated by an arithmetic mean roughness Ra of 0.5 μm to 10 μm on the surface thereof, and the encapsulating material may sometimes contain a release agent for the convenience of extraction from the frame of the packaging device. Therefore, when the adhesive surface is adhered to the resin package surface, the fixing function may not be fully utilized.

In the use of the dicing sheet according to the embodiment, the adhesive layer (i.e., the reverse side of the substrate surface of the adhesive layer) is adhered to the resin package surface of the semiconductor component (mold assembly). Further, in the case where the release sheet is adhered to the adhesive sheet layer of the dicing sheet, the release sheet is peeled off to expose the adhesive layer, and the surface may be adhered to the resin package surface of the semiconductor component. The outer edge of the dicing sheet is adhered to the adhesive layer, which is usually formed in the portion, and adhered to a ring called a ring frame for fixing or ringing, since the adhesive layer is properly bonded. The composition of the agent is formed, so the TACK value is also appropriate. Therefore, it is also possible to reduce the possibility that the mold wafer formed by the chipping of the semiconductor component is scattered during processing.

The size of the mold wafer formed by the cutting process is usually 5 mm × 5 mm or less, and although there is a case where the system is about 1 mm × 1 mm recently, The adhesive layer of the dicing sheet according to the embodiment can sufficiently cope with the cutting of the base pitch because the TACK value is appropriate.

By implementing the above cutting process, a plurality of mold wafers can be obtained from the semiconductor component. After the end of the cutting process, in order to facilitate the ejection of a plurality of mold wafers disposed around the dicing sheet, the dicing sheet is usually subjected to an extended stretching process in a direction in the main surface. The extent of this extension can be determined by considering the spacing required for the adjacent mold wafers and the extent of the elongation of the substrate.

After the extension process is performed, a mold wafer is taken up on the adhesive layer by a conventional method such as a collet, and the top mold wafer is supplied to a next process such as a conveyance process.

After the completion of the dicing process and the start of the ejector process, when the energy ray is irradiated on the substrate side of the dicing sheet according to the present embodiment, the energy ray polymerizable group contained in the viscous layer of the dicing sheet reacts. The adhesiveness of the adhesive layer on the surface of the mold wafer can be lowered. Further, since the adhesive layer having the dicing sheet according to the present embodiment is formed by a suitable adhesive composition, the material constituting the adhesive layer is difficult in the depressed portion of the resin package surface of the semiconductor component of the adhesive body. enter. Therefore, the force required to separate the material entering the depressed portion from the depressed portion during the ejector or the force required to break the material to separate it from the adhesive layer is difficult to increase. Therefore, the dicing sheet according to the present embodiment is particularly difficult to cause a plucking failure.

As described above, in the method of manufacturing a mold wafer according to the present embodiment, wafer scattering is less likely to occur, and it is difficult to cause a topping failure in the subsequent process. Therefore, after the cutting process and the topping process of dividing the mold component such as the semiconductor component into a plurality of die wafers, in a series of processes up to the next process The yield is also difficult to reduce. Therefore, the mold wafer obtained by the manufacturing method according to the present embodiment of the dicing sheet according to the present embodiment is easy to form a cost advantage. In addition, there are cases in which wafer scattering and topping failure occur, and the wafers other than the mold wafer directly related to the defects are defective in the mold wafer manufactured on the same path due to collision or the like. Therefore, the mold wafer manufactured by the method for manufacturing a mold wafer according to the present embodiment can reduce the possibility of occurrence of such a problem and is excellent in quality.

The embodiments described above are described in order to facilitate understanding of the present invention, and are not intended to limit the present invention. Therefore, all the design elements disclosed in the above embodiments are included in all design changes or equivalents thereof within the technical scope of the present invention.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and the like, but the scope of the present invention is not limited by these Examples and the like.

(Example 1)

(1) Modulation of coating liquid

A coating liquid having the following composition was prepared.

75 parts by mass of 2-ethylhexyl acrylate and 10 parts by mass of methyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (HEA) are polymerized to obtain copolymerization as an acrylic polymer (A1). (weight average molecular weight of 700,000 in terms of polystyrene).

As the compound (A2), isocyanoethyl methacrylate (MOI), and the above-mentioned acrylic polymer (A1) as an organometallic catalyst (C), a zirconium clamp catalyst (MATSUMOTO FINE CHEMICAL CO., LTD., In the presence of "ZC-700"), it reacts. The amount of the compound (A2) to be used is a monomer (m1) which is a constituent unit of a hydrogen group having a reactive functional group of the acrylic polymer (A1), and is equivalent to 0.6 equivalent of the HEA of the position-providing. The amount of addition of the organic metal catalyst (C) is 0.1 part by mass based on 100 parts by mass of the solid content of the acrylic polymer (A1). Through the above reaction, a product containing a component based on the acrylic polymer (A) and the organic metal catalyst (C) was obtained.

0.3 parts by mass of the isocyanate bridging agent (B) ("BHS-8515", manufactured by TOYOCHEM CO., LTD.), and 3.0, when the amount of the acrylic polymer (A) in the product and the product is 100 parts by mass. The mass fraction of the photoinitiator (D) ("IRUGACURE (registered trademark) 184", manufactured by BASF Corporation) was mixed (all the blending ratios were converted according to the solid content) to obtain a binder composition.

(2) Production of cutting pieces

A release sheet having a release surface (formed by Lintec Corporation, "SP-PET381031") prepared by forming a release layer of a silicone resin on one surface of a polyethylene terephthalate base film having a thickness of 38 μm. Applying the coating liquid described above to the peeling surface of the release sheet by a knife coater, and curing the obtained coating film and each of the release sheets in an environment of 100 ° C for 1 minute. The coating film was dried while being subjected to a bridging reaction to obtain a laminate formed of a release sheet and an adhesive layer (thickness: 10 μm).

Adhesive layer of the above-mentioned laminated body was adhered to one side of the substrate (completed corona treatment, surface tension: 54 mN/m) formed of an ethylene-methacrylic acid copolymer (EMAA) film having a thickness of 140 μm. The dicing sheet formed by the substrate and the adhesive layer has a state in which the release sheet has more layers on the adhesive layer.

(Example 2)

The organometallic catalyst (C) used for obtaining the acrylic polymer (A) was replaced with a titanium clamp catalyst (Zumumi clamp catalyst) ("TCSUM"), manufactured by MATSUMOTO FINE CHEMICAL CO., LTD. -750"), the amount of use of the acrylic polymer (A1) is 0.03 parts by mass based on 100 parts by mass of the solid content of the acrylic polymer (A1), and the state of laminating the release sheet on the adhesive layer after performing the same operation as in Example 1 The cut piece is obtained.

(Comparative Example 1)

The organometallic catalyst (C) used for obtaining the acrylic polymer (A) is replaced with a tin catalyst ("BXX-3778", manufactured by TOYOCHEM CO., LTD.) without using a zirconium clamp catalyst. The amount thereof used is 0.03 parts by mass based on 100 parts by mass of the solid content of the acrylic polymer (A1). Further, the same operation was carried out as in Example 1, and a dicing sheet was obtained in a state where a release sheet was laminated on the adhesive layer.

(Example 3)

The amount of MOI used as the compound (A2) used for obtaining the acrylic polymer (A) was 0.7 equivalent of the HEA system. Further, the same operation was carried out as in Example 1, and a dicing sheet was obtained in a state where a release sheet was laminated on the adhesive layer.

(Example 4)

The amount of MOI used as the compound (A2) used for obtaining the acrylic polymer (A) was 0.9 equivalent of the HEA system. Further, the same operation was carried out as in Example 1, and a dicing sheet was obtained in a state where a release sheet was laminated on the adhesive layer.

(Comparative Example 2)

As the compound (A2) used for obtaining the acrylic polymer (A) The amount of MOI used was 0.3 equivalent for the HEA system. Further, the same operation was carried out as in Example 1, and a dicing sheet was obtained in a state where a release sheet was laminated on the adhesive layer.

(Comparative Example 3)

The thickness of the adhesive layer was carried out at 30 μm. Further, the same operation was carried out as in Example 1, and a dicing sheet was obtained in a state where a release sheet was laminated on the adhesive layer.

(Comparative Example 4)

After copolymerizing 85 parts by mass of 2-ethylhexyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate, a copolymer (weight average molecular weight of 700,000 in terms of polystyrene) was obtained. Here, the copolymer is not used instead of the acrylic polymer (A1). Further, the same operation was carried out as in Example 1, and a dicing sheet was obtained in a state where a release sheet was laminated on the adhesive layer.

(Comparative Example 5)

The adhesive composition was prepared in the manner described below. Further, the same operation was carried out as in Example 1, and a dicing sheet was obtained in a state where a release sheet was laminated on the adhesive layer.

When the copolymer is 100 parts by mass, 10 parts by mass of the bridging agent and 40 parts by mass of the energy ray-curable compound (the amount of the solid content of the solid content) are added to obtain a binder coating composition as a solution of the organic solvent. .

The details of the above copolymer, bridging agent and energy ray-curable compound are as follows: copolymer: 2-ethylhexyl acrylate/methyl acrylate/acrylic acid = 50/40/10 composition ratio, polystyrene-equivalent weight average molecular weight :800 000

Bridging agent: toluene diisocyanate-trimethylolpropane (TDI-TMP), TOYOCHEM CO., LTD., "BHS 8515"

Energy ray-curable compound: 10-functional urethane acrylate, molecular weight: 1700, manufactured by NIPPON SYNTHETIC CHEMICAL INDUSTRY CO., LTD., "UV-1700B"

(Test Example 1) <Evaluation of wafer scattering>

An analog semiconductor device having an arithmetic mean roughness Ra of 1 μm on the surface of the package resin was produced by using a resin for a semiconductor module ("G700" manufactured by SUMITOMO BAKELITE CO., LTD.) at 50 mm × 50 mm and a thickness of 600 μm. According to the above-described examples and comparative examples, the adhesive layer of the manufactured dicing sheet was adhered to the encapsulating resin surface of the dummy semiconductor device produced as described above by a film coater ("Adwill RAD 2500" manufactured by Lintec Corporation). The dicing sheet obtained in this way and the laminated body other than the analog semiconductor module were placed in a circular frame for cutting ("2-6-1", manufactured by DISCO CORPORATION), and then a cutting device ("DID-651", manufactured by DISCO CORPORATION) The cutting process for performing the cutting on the surface of the dummy semiconductor component is divided into mold chips having a size of 1 mm × 1 mm. In addition, the cutting conditions are as follows: Cutting knife: manufactured by DISCO CORPORATION, "ZBT-5074 (Z1110LS3)"

Cutting blade thickness: 0.17mm

Cutting knife protrusion amount: 3.3mm

Cutting knife speed: 30000rpm

Cutting speed: 100mm/min

Notch depth to substrate: 50μm

Cutting water volume: 1.0L/min

Cutting water temperature: 20 ° C

The number of mold wafers that are removed from the cutting piece in the cutting process by visually observing the member made by adhering the mold wafer to the adhesive layer of the dicing sheet obtained by the cutting process, and dividing the number of the dies by the cutting The wafer scattering rate (unit: %) is obtained after the number of divisions of the process. When the wafer scattering rate is less than 10%, it is judged to be good, and when it is 10% or more, it is judged to be defective. The results are shown in Table 1. In Table 1, "A" means that the judgment is good, and "B" means that the judgment is bad.

Further, in the wafer group in which the dicing sheet was sliced and diced, five columns in a row and five columns in a row were randomly selected, and 250 mold wafers were selected, and 150 die wafers were additionally selected as the measurement target wafer. The side surface of these measurement target wafers was observed under a microscope, and it was examined whether or not adhesive agglomerates of 10 μm or more adhered to the side surface of the mold wafer to determine whether or not residual glue was generated. The results are shown in Table 1. In Table 1, "A" indicates that the judgment is good (no residual glue is generated), and "B" indicates that the judgment is bad (residual residual rubber is generated).

(Test Example 2) <Evaluation of short-term and long-term aggressiveness>

An analog semiconductor package having an arithmetic mean roughness Ra of 1 μm on the surface of the package resin was produced by using a resin for a semiconductor module ("G700" manufactured by SUMITOMO BAKELITE CO., LTD.) at 50 mm × 50 mm and a thickness of 600 μm . According to the above-described examples and comparative examples, the adhesive layer of the manufactured dicing sheet was obtained by sticking a film-molding machine ("AdwillRAD 2500" manufactured by Lintec Corporation) to the encapsulating resin surface of the analog semiconductor device produced as described above. A laminated body other than the dicing sheet and the analog semiconductor module is placed in a circular frame for cutting ("2-6-1" manufactured by DISCOCORCATION), and the semiconductor device is molded by a dicing device ("DFD-651" manufactured by DISCOCORCATION). The cutting process for cutting on the surface was divided into mold chips having a size of 10 m × 10 mm. In addition, the cutting conditions are as follows: Cutting knife: manufactured by DISCO CORPORATION, "ZBT-5074 (Z1110LS3)"

Cutting blade thickness: 0.17mm

Cutting knife protrusion amount: 3.3mm

Cutting knife speed: 30000rpm

Cutting speed: 100mm/min

Notch depth to substrate: 50 μ m

Cutting water volume: 1.0L/min

Cutting water temperature: 20 ° C

After the completion of the above-mentioned dicing process, the substrate side of the dicing sheet after the dicing process was irradiated with an ultraviolet ray irradiation apparatus (RAD-2000m/12, manufactured by Lintec Corporation) in a state of no relaxation, and was irradiated under a nitrogen atmosphere (illuminance 230 mW/ Cm ² , light quantity 190 mJ/cm ² ).

After the ultraviolet ray irradiation, the dicing sheet of the member formed by attaching the mold wafer to the side of the adhesive layer of the dicing sheet was used at a speed of 1 mm/ by an extension device ("ME-300B type" manufactured by JCM Co., Ltd.). The sheet is subjected to an extension process to extend 20 mm in the circumferential direction.

Next, 100 die wafers placed on the dicing sheet were subjected to a topping test to evaluate the topping property (short term). That is, for the portion of the mold wafer which is the object of the dicing sheet to be contacted, the top side of the substrate is 1.5 mm on the needle, and the opposite side of the opposite side of the dicing sheet of the protruding mold wafer is adhered to the vacuum collet (Collet). ), lifting the mold wafer adhered to the vacuum collet. The topping (short term) can be evaluated using the following criteria. The results are shown in Table 1.

A: The topping is successful, and the material forming the adhesive does not adhere to the opposite side of the adhesive layer of the top mold wafer.

B: The topping is successful. On the top of the mold wafer, although the opposite surface of the adhesive layer adheres to the material composed of the adhesive, the adhesion of the above substances cannot be recognized on most of the mold wafers.

C: The topping is successful, and the material forming the adhesive agent is mostly present on the opposite side of the adhesive layer of the top mold wafer.

D: I can't take it.

After the completion of the dicing process, the time until the ultraviolet ray irradiation was 30 days, and the same operation as the evaluation of the above-mentioned topping property (short term) was performed, and in the above A, the topping property (long term) was evaluated on the basis of D. The results are shown in Table 1.

(Test Example 3) <Measurement of TACK Value>

For the surface before the energy ray irradiation of the adhesive layer of the dicing sheet manufactured in the examples and the comparative examples, a probe having a diameter of 5 mm (5 mm ψ) was used as a probe type initial adhesion tester (manufactured by RHESCA CORPORATION). , "RPT-100") measurement. In the method described in JIS Z0237:1991, the peeling speed was changed to 1 mm/min, and the load system was 100 gf/cm ² and the contact time was 1 second, which was carried out according to the description of the JIS regulations. The amount of measured energy (peak integrated value) is obtained as the TACK value (unit: mJ/5 mm ψ). The results are shown in Table 1.

(Test Example 4) <Measurement of Thickness of Adhesive Layer>

The adhesive compositions used in the examples and the comparative examples were coated on one side of a polyethylene terephthalate film having a thickness of 38 μm under the same conditions as in the examples and the comparative examples. Dry to obtain the product formed by the film and the adhesive layer Layer body. The thickness of the laminate was measured by a thickness constant pressure measuring device ("PG-02J", manufactured by TECLOCK CORPORATION), and the thickness of the film was obtained by subtracting the thickness of the film from the obtained measurement values (unit: μm). The results are shown in Table 1.

(Test Example 5) <Measurement of elastic modulus before irradiation and modulus of elasticity after irradiation>

The adhesive composition used in the examples and the comparative examples was dried on a release surface of a 38 μm-thick release film ("SP-PET381031" manufactured by Lintec Corporation), and then coated to have a thickness of 40 μm, and then The obtained coating film and the laminate formed of the release film were kept at 100 ° C for 1 minute to dry the coating film. A plurality of adhesive layers on the release film formed in this order were prepared, and a laminated layer having a thickness of 800 μm was formed, and a circular hole having a diameter of 10 mm was drilled as a sample for measurement. Then, a sample having a frequency of 1 Hz was applied to the sample by a bonding measuring device ("ARES" manufactured by TA INSTRUTMENTS Co., Ltd.), and a storage modulus of -50 to 150 ° C was measured to obtain a numerical value as a storage modulus at 23 ° C. Modulus (unit: kPa). The results are shown in Table 1.

As described above, the adhesive layer formed in the adhesive composition used in the examples and the comparative examples was obtained by laminating a film on the release film, and an ultraviolet irradiation device (RAD-2000m, manufactured by Lintec Corporation) was used for the member. / 12), in the release film side of the ultraviolet irradiation member embodiment (illuminance 230mW / cm ^2, light quantity of 190mJ / cm ²⁾ under an atmosphere of nitrogen. After the ultraviolet irradiation, the member was subjected to the same operation as the measurement of the elastic modulus before the irradiation, and the storage modulus value at 23 ° C was obtained as the elastic modulus after irradiation (unit: MPa). The results are shown in Table 1.

As shown in Table 1, in the cutting process and the topping process, the dicing sheet of the embodiment satisfying the conditions of the present invention is not easy to occur, and in particular, the dicing sheets manufactured in the embodiments 1 to 3 are not only short-term plucking. Excellent and long-term superiority. Even if the period from the cutting process to the ultraviolet irradiation is 30 days, all the die wafers provided in the topping test can be topped out.

[Industrial availability]

The dicing sheet according to the present invention is suitable for use as a dicing sheet of a mold assembly having a large unevenness of an adhesive surface.

Claims (7)

A dicing sheet comprising a substrate and an adhesive layer laminated on at least one side of the substrate, wherein the adhesive layer is composed of an acrylic polymer having an energy ray polymerizable group and a reactive functional group. (A), and an adhesive composition of an isocyanate-based bridging agent (B) capable of bridging reaction with the above reactive functional group; the acrylic polymer (A) is an acrylic having the above reactive functional group The polymer (A1), and the isocyanate compound (A2) having the above energy ray-polymerizable group are obtained by reacting in the presence of an organometallic catalyst (C) containing at least one of titanium and zirconium; the above adhesive layer The storage modulus at 23 ° C is 50 kPa or more and 80 kPa or less in the state before the irradiation of the energy ray, and is 5.0 MPa or more in the state after the irradiation of the energy ray, and the thickness of the above-mentioned adhesive layer is less than 20 μm. In the state described in JIS Z0237:1991, the surface of the adhesive layer is in the state described in JIS Z0237:1991, and the probe-type initial tack tester (Probe tack) is used under the condition that the peeling speed is changed to 1 mm/min. Measured More than the amount of energy based 0.1mJ / 5mm ψ, 0.8mJ / 5mm ψ less. According to the dicing sheet of the first aspect of the invention, the storage modulus of the adhesive layer at 23 ° C is 500 MPa or less in a state after the irradiation of the energy ray. The dicing sheet according to claim 1 or 2, wherein the acrylic polymer (A1) is provided with a monomer (m1) having a constituent unit of the above reactive functional group for providing the above acrylic polymer ( A1) the whole monomer, The mass ratio is 5% by mass or more and 30% by mass or less. In the reaction for forming the acrylic polymer (A), the amount of the compound (A2) used is 0.4 equivalent or more and 0.9 equivalent to the monomer (m1). the following. The dicing sheet according to claim 1 or 2, wherein the organometallic catalyst (C) comprises a zirconium tong compound. The dicing sheet according to claim 1 or 2, wherein, in use, a semiconductor component in which a semiconductor wafer is encapsulated by a resin is adhered to a reverse surface of the substrate surface of the adhesive layer Resin encapsulation surface. A method for producing a dicing sheet comprising a substrate and a dicing sheet of an adhesive layer laminated on at least one side of the substrate; characterized by comprising: an energy ray-polymerizable group and a reactivity A functional group-based acrylic polymer (A) and an adhesive composition of an isocyanate-based bridging agent (B) capable of bridging the reactive functional group, coated on one side of the substrate, and obtained by coating Forming the adhesive layer to obtain the dicing sheet; and applying the adhesive composition to the release sheet peeling surface, forming the adhesive layer from the obtained coating film, and the above-mentioned adhesive sheet a surface of the adhesive layer opposite to the surface opposite to the release sheet is adhered to one surface of the substrate, and the dicing sheet is at least one of a process of adhering the release sheet to the adhesive layer; The acrylic polymer (A) contains titanium and zirconium from an acrylic polymer (A1) having the above reactive functional group and an isocyanate compound (A2) having the above energy ray polymerizable group. The reaction of the obtained at least the presence of an organometallic catalyst of (C) of; provided above acrylic polymer (A1) in The monomer (m1) of the constituent unit containing the reactive functional group is 5% by mass or more and 30% by mass or less based on the total amount of the monomer providing the acrylic polymer (A1); In the reaction of the polymer (A), the amount of the compound (A2) used is 0.4 equivalent or more and 0.9 equivalent or less to the monomer (m1), and the thickness of the adhesive layer is less than 20 μm. The storage modulus of the layer at 23 ° C is 50 kPa or more and 80 kPa or less in the state before the irradiation of the energy ray, and is 5.0 MPa or more in the state after the irradiation of the energy ray; before the surface of the above-mentioned adhesive layer is irradiated with the energy ray In the method described in JIS Z0237:1991, the amount of energy measured using a probe-type initial tack tester (Probe tack) is 0.1 mJ/5 mm under the condition that the peeling speed is changed to 1 mm/min. Above, 0.8mJ/5mm ψ below. A manufacturing method for adhering the adhesive layer of the dicing sheet according to claim 1 or 2 to the resin sealing surface of the mold assembly, and cutting the mold assembly on the dicing sheet to obtain a sheet A method of manufacturing a mold wafer of a plurality of mold wafers.