TW202142652A - Sheet for semiconductor device fabrication - Google Patents

Abstract

A sheet for semiconductor device fabrication comprising: a base material, a pressure-sensitive adhesive layer, an intermediate layer, and a film-shaped adhesive, the sheet being configured by laminating the pressure-sensitive adhesive layer, the intermediate layer, and the film-shaped adhesive in this order on the base material, and the intermediate layer including a non-silicone resin having a weight average molecular weight of 100,000 or less as a main component.

Description

Sheet for semiconductor device manufacturing

The present invention relates to a sheet for manufacturing semiconductor devices. This case claims priority based on Special Application No. 2020-058734 filed in Japan on March 27, 2020, and its content is incorporated in this specification.

In the manufacture of a semiconductor device, a semiconductor wafer with a film-like adhesive which is provided with a semiconductor wafer and a film-like adhesive provided on the inner surface of the semiconductor wafer is used. As an example of the manufacturing method of the semiconductor wafer with a film-like adhesive agent, the following can be mentioned, for example.

That is, firstly, a dicing die is attached to the inner surface of the semiconductor wafer. Examples of the dicing bond wafer include a dicing bond wafer provided with a support sheet and a film-like adhesive provided on one surface of the support sheet. The support sheet can be used as a dicing sheet. As the supporting sheet, there are a plurality of supporting sheets with different configurations, for example, a supporting sheet provided with a substrate and an adhesive layer provided on one surface of the aforementioned substrate; a supporting sheet composed of only the substrate, and the like. With a support sheet with an adhesive layer, the outermost surface on the side of the adhesive layer will be the surface where the film-like adhesive is placed. The dicing die is attached to the inner surface of the semiconductor wafer by the film-like adhesive in it.

Secondly, the semiconductor wafer on the support sheet and the film-like adhesive are cut together by dicing with a blade. The "cutting" of a semiconductor wafer is also called "division", whereby the semiconductor wafer is singulated into a target semiconductor wafer. The film-like adhesive is cut along the outer periphery of the semiconductor wafer. Thereby, a semiconductor wafer with a film-like adhesive formed by a semiconductor wafer and a film-like adhesive disposed on the inner surface of the semiconductor wafer is obtained, and a plurality of semiconductor wafers with the film-like adhesive are obtained on the support sheet A group of semiconductor wafers with a film-like adhesive which are maintained in a neatly arranged state.

Secondly, the semiconductor wafer with the film-like adhesive is pulled away from the supporting sheet and picked up. When using a support sheet with a hardenable adhesive layer, at this time, by hardening the adhesive layer to reduce the adhesiveness in advance, picking up becomes easy. Through the above method, a semiconductor chip with a film-like adhesive used in the manufacture of a semiconductor device is obtained.

As another example of the manufacturing method of the semiconductor wafer with a film-like adhesive agent, the following can be mentioned, for example. That is, first, a back polishing tape (sometimes called "surface protection tape") is attached to the circuit formation surface of the semiconductor wafer. Secondly, a predetermined segmentation part is set inside the semiconductor wafer, the area included in the part is set as the focus, and the laser light is irradiated to focus on the focus, thereby forming a modified layer inside the semiconductor wafer. Second, use a grinder to grind the inner surface of the semiconductor wafer, adjust the thickness of the semiconductor wafer to a target value, and use the grinding force applied to the semiconductor wafer at this time to form the modified layer The semiconductor wafer is divided (singulated) to produce a plurality of semiconductor wafers. This method of dividing a semiconductor wafer with the formation of a modified layer is called stealth dicing (registered trademark), which is the same as irradiating the semiconductor wafer with laser light to remove the semiconductor wafer in the irradiated part, and gradually start from the surface. Laser cutting for cutting semiconductor wafers is completely different in nature.

Next, one sticky wafer is attached to the inner surface (in other words, the ground surface) of all the semiconductor wafers that are fixed on the back polishing tape after the above-mentioned grinding. The bonding chip can be the same as the above-mentioned dicing bonding chip. The sticky chip can be designed so that it is not only used in the dicing of semiconductor wafers but has the same structure as the dicing sticky chip. The adhesive chip is also attached to the inner surface of the semiconductor chip by the film-like adhesive in it.

Secondly, after removing the back polishing tape from the semiconductor wafer, while cooling the bonded wafer, stretch the surface of the bonded wafer (for example, the surface where the film-like adhesive is attached to the semiconductor wafer) in the parallel direction, that is, the so-called The expansion (cold expansion) cuts the film-like adhesive along the outer periphery of the semiconductor wafer. By the above method, a semiconductor wafer with a film-like adhesive formed by a semiconductor wafer and a cut-off film-like adhesive provided on the inner surface of the semiconductor wafer is obtained.

Secondly, as in the case of cutting with a blade as described above, the semiconductor wafer with the film-like adhesive is separated from the supporting sheet and picked up, thereby obtaining the semiconductor wafer with the film-like adhesive used in the manufacture of semiconductor devices.

Both dicing and bonding chips can be used to manufacture semiconductor chips with film-like adhesives, and ultimately achieve the goal of manufacturing semiconductor devices. In this specification, dicing and bonding chips are referred to as "sheets for manufacturing semiconductor devices".

As a sheet for manufacturing semiconductor devices, for example, a dicing die-bonding tape (equivalent to the aforementioned dicing tape) having a substrate layer (equivalent to the aforementioned support sheet) and an adhesive layer (equivalent to the aforementioned film-like adhesive) laminated in direct contact with each other is disclosed. Sticky wafer) (see Patent Document 1). Since the 90 degree peeling force of the base material layer and the adhesive layer at -15°C is adjusted to a specific range for this dicing die-bonding tape, the adhesive layer can be divided with high precision by expansion. In addition, because the base layer and the adhesive layer The 90-degree peeling force of the adhesive layer at 23°C is adjusted to a specific range. Therefore, when using this dicing die bonding tape, the semiconductor wafer with the adhesive layer (equivalent to the aforementioned semiconductor with the film-like adhesive can be picked up without difficulty). Wafer), and during the pick-up process, the semiconductor wafer and the semiconductor wafer can be prevented from peeling off the adhesive layer. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2018-56289.

[The problem to be solved by the invention]

However, although the dicing die-bonding tape disclosed in Patent Document 1 is suitable for stealth cutting (registered trademark), it is not suitable for blade cutting. If this dicing die-bonding tape is used for blade dicing, it is easy to generate whisker-like cutting chips from the substrate layer (sometimes called "Whisker" in this field), which is suitable for dividing semiconductor wafers. Difference.

The object of the present invention is to provide a sheet for manufacturing a semiconductor device which is excellent in the suitability for dividing a semiconductor wafer. [Means to solve the problem]

The present invention provides a sheet for manufacturing semiconductor devices, comprising a substrate, an adhesive layer, an intermediate layer, and a film adhesive; the adhesive layer, the intermediate layer, and the film adhesive are sequentially laminated on the substrate The intermediate layer contains a non-silicone resin with a weight average molecular weight of 100,000 or less as a main component. In the semiconductor device manufacturing sheet of the present invention, when the film-like adhesive side of the intermediate layer is analyzed by X-ray photoelectron spectroscopy, the concentration of silicon is relative to carbon, oxygen, nitrogen, and silicon. The ratio of the total concentration can be 1% to 20%. In the semiconductor device manufacturing sheet of the present invention, it is preferable that the intermediate layer contains an ethylene-vinyl acetate copolymer and a silicone compound as the non-silicon-based resin. In the ethylene-vinyl acetate copolymer, The ratio of the mass of the constituent units derived from vinyl acetate to the total mass of all constituent units is 10% to 40% by mass. In the intermediate layer, the content of the ethylene-vinyl acetate copolymer is relative to the total mass of the intermediate layer. The mass ratio is 90% to 99.99% by mass, and the ratio of the content of the silicone compound in the intermediate layer to the total mass of the intermediate layer is 0.01% to 10% by mass. [Efficacy of invention]

According to the present invention, there is provided a sheet for manufacturing a semiconductor device which is excellent in the suitability for dividing a semiconductor wafer.

◇Semiconductor device manufacturing sheet A sheet for manufacturing a semiconductor device according to an embodiment of the present invention includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive; the adhesive layer, the intermediate layer, and the film are sequentially laminated on the substrate The intermediate layer contains a non-silicone resin with a weight average molecular weight of 100,000 or less as the main component.

When the semiconductor device manufacturing sheet of this embodiment is used as a dicing sticky wafer for blade dicing, since the semiconductor device manufacturing sheet is provided with the intermediate layer, it is easy to prevent the blade from reaching the substrate and suppress the generation of whiskers from the substrate. Shaped cutting chips (alias: Whisker, hereinafter, not limited to those derived from the base material, but sometimes simply referred to as "cutting chips"). In addition, since the main component of the intermediate layer cut by the blade is a non-silicon resin with a weight average molecular weight of 100,000 or less, especially a weight average molecular weight of 100,000 or less, the generation of cutting chips from the intermediate layer can also be suppressed.

On the other hand, when the semiconductor device manufacturing sheet of this embodiment is used as a bonding wafer, and the dicing (invisible dicing (registered trademark)) accompanying the formation of a modified layer on the semiconductor wafer is performed, due to the aforementioned semiconductor device manufacturing The sheet is equipped with the aforementioned intermediate layer, and by successively stretching the sheet for manufacturing the semiconductor device in a direction parallel to the surface of the sheet for manufacturing the semiconductor device (for example, the attaching surface of the film-like adhesive to the semiconductor wafer), that is, By performing so-called expansion, the film-like adhesive is cut with high precision at the target site, and cutting failures can be suppressed.

In this way, the semiconductor device manufacturing sheet of the present embodiment can suppress the generation of cutting chips from the base material and the intermediate layer during the blade dicing, can suppress the cutting failure of the film-like adhesive during the aforementioned expansion, and can suppress the division of the semiconductor wafer The characteristics that sometimes occur in poor conditions are excellent in the suitability of semiconductor wafer division.

In the present specification, the "weight average molecular weight" is a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless it is particularly limited.

The method of using the semiconductor device manufacturing sheet of this embodiment will be described in detail later.

Hereinafter, the sheet for manufacturing a semiconductor device of this embodiment will be described in detail with reference to the drawings. In addition, the figures used in the following description are sometimes enlarged and displayed as the main part in order to easily understand the characteristics of the present invention, and the size ratio of each component may not be the same as the actual one.

FIG. 1 is a cross-sectional view schematically showing a sheet for manufacturing a semiconductor device according to an embodiment of the present invention, and FIG. 2 is a plan view of the sheet for manufacturing a semiconductor device shown in FIG. 1. In addition, in the figures following FIG. 2, for the same constituent elements as those shown in the already-explained figures, the same reference numerals as those in the already-explained figures are assigned, and detailed explanations are omitted.

The sheet 101 for manufacturing a semiconductor device shown here is provided with a base material 11, and an adhesive layer 12, an intermediate layer 13, and a film-like adhesive 14 are laminated on the base material 11 in this order. The sheet 101 for manufacturing a semiconductor device further includes a release film 15 on a surface (hereinafter, sometimes referred to as "first surface") 14a on the side opposite to the side where the intermediate layer 13 of the film-like adhesive 14 is provided.

The sheet 101 for manufacturing a semiconductor device is provided with an adhesive layer 12 on one side of the substrate 11 (sometimes referred to as the "first side" in this specification) 11a, and the adhesive layer 12 is opposite to the side on which the substrate 11 is provided The side surface (sometimes referred to as the "first surface" in this specification) 12a is provided with an intermediate layer 13, and the surface on the opposite side to the side where the adhesive layer 12 is provided on the intermediate layer 13 (sometimes referred to in this specification as (Referred to as "first surface") 13a is provided with a film-like adhesive 14 and a release film 15 is provided on the first surface 14a of the film-like adhesive 14. In this way, the sheet 101 for manufacturing a semiconductor device is composed of a base material 11, an adhesive layer 12, an intermediate layer 13, and a film-like adhesive 14 layered in this order in the thickness direction.

In the semiconductor device manufacturing sheet 101 with the release film 15 removed, the first surface 14a of the film-like adhesive 14 is attached to a semiconductor wafer, a semiconductor wafer, or a semiconductor wafer that is not completely divided (The illustration is omitted).

In this specification, regardless of whether it is a semiconductor wafer or a semiconductor wafer, the surface on which the circuit is formed is referred to as the "circuit formation surface", and the surface on the opposite side of the circuit formation surface is referred to as the "inner surface".

In this specification, a laminate having a structure in which a base material and an adhesive layer are laminated in the thickness direction and an intermediate layer is not laminated may be referred to as a "support sheet". The reference numeral 1 in Fig. 1 indicates a support sheet. In addition, a laminate in which a substrate, an adhesive layer, and an intermediate layer are sequentially laminated in the thickness direction is sometimes referred to as a "laminated sheet." In Fig. 1, the symbol 10 indicates a laminated sheet. The laminate of the support sheet and the intermediate layer is included in the laminate sheet.

The intermediate layer 13 and the film-like adhesive 14 are all circular in plan when viewed from above, and the diameter of the intermediate layer 13 is the same as the diameter of the film-like adhesive 14. In addition, in the sheet 101 for manufacturing a semiconductor device, the intermediate layer 13 and the film-like adhesive 14 are aligned in this isocenter. In other words, the outer peripheral positions of the intermediate layer 13 and the film-like adhesive 14 are all aligned in these radial directions. The way to configure it.

The areas of the first surface 13a of the intermediate layer 13 and the first surface 14a of the film-like adhesive 14 are smaller than those of the first surface 12a of the adhesive layer 12. In addition, the maximum value (that is, the diameter) of the width W ₁₃ of the intermediate layer 13 and the maximum value (that is, the diameter) of the width W ₁₄ of the film-like adhesive 14 are higher than the maximum value of the width of the adhesive layer 12 and the substrate 11 The maximum value of the width is too small. Therefore, in the sheet 101 for manufacturing a semiconductor device, a part of the first surface 12 a of the adhesive layer 12 is not covered by the intermediate layer 13 and the film-like adhesive 14. In this way, the area where the intermediate layer 13 and the film-like adhesive 14 are not laminated on the first surface 12a of the adhesive layer 12 is in direct contact with the release film 15 and is laminated. When the release film 15 is removed, this area Exposed state (hereinafter, this area may be referred to as "non-laminated area" in this specification). In addition, in the semiconductor device manufacturing sheet 101 provided with the release film 15, the area of the adhesive layer 12 that is not covered by the intermediate layer 13 and the film-like adhesive 14 may be an area where the release film 15 is not laminated as shown here. , Or there is no such area.

The semiconductor device manufacturing sheet 101 in a state where the film-like adhesive 14 is not cut and is attached to the above-mentioned semiconductor wafer or semiconductor chip, etc. by using the film-like adhesive 14 A part of the aforementioned non-layered area is attached to and fixed by a jig such as a ring frame for fixing a semiconductor wafer. Therefore, it is not necessary to separately provide a jig adhesive layer for fixing the semiconductor device manufacturing sheet 101 to the aforementioned jig in the semiconductor device manufacturing sheet 101. In addition, since there is no need to provide an adhesive layer for a jig, the sheet 101 for manufacturing a semiconductor device can be manufactured inexpensively and efficiently.

In this way, although the sheet 101 for manufacturing a semiconductor device can exhibit an advantageous effect by not having an adhesive layer for a jig, it may also have an adhesive layer for a jig. In this case, the adhesive layer for a jig may be provided in the area near the peripheral edge of the surface of one of the layers of the sheet 101 for manufacturing a semiconductor device. Examples of such a region include the aforementioned non-laminated region in the first surface 12a of the adhesive layer 12, and the like.

The adhesive layer for a jig may be a well-known one, for example, may have a single-layer structure containing an adhesive component, or may have a multiple-layer structure in which layers of the adhesive component are contained on the two-area layers of the sheet to be the core material.

In addition, as described later, when the sheet 101 for manufacturing a semiconductor device is stretched in a parallel direction with respect to the surface of the sheet 101 for manufacturing a semiconductor device (for example, the first surface 12a of the adhesive layer 12), that is, when the so-called expansion is performed The presence of the aforementioned non-laminated area on the first surface 12a of the adhesive layer 12 makes it possible to easily expand the sheet 101 for manufacturing a semiconductor device. In addition, not only can the film-like adhesive 14 be easily cut, but also the separation of the intermediate layer 13 and the film-like adhesive 14 from the adhesive layer 12 can be suppressed in some cases.

In the sheet 101 for manufacturing a semiconductor device, the intermediate layer 13 contains a non-silicon-based resin having a weight average molecular weight of 100,000 or less as a main component.

The semiconductor device manufacturing sheet of the present embodiment is not limited to those shown in FIGS. 1 and 2. Partial configuration changes and deletions can be made to those shown in FIGS. 1 and 2 within the scope that does not impair the efficacy of the present invention. Or append.

For example, the sheet for manufacturing a semiconductor device of the present embodiment may include other layers that do not correspond to any of the base material, the adhesive layer, the intermediate layer, the film-like adhesive, the release film, and the adhesive layer for jigs. However, the semiconductor device manufacturing sheet of the present embodiment preferably has an adhesive layer in direct contact with the base material as shown in FIG. A film-like adhesive is provided in the state of being directly in contact with the intermediate layer.

For example, in the semiconductor device manufacturing sheet of this embodiment, the planar shape of the intermediate layer and the film-like adhesive may be a shape other than a circular shape, and the planar shapes of the intermediate layer and the film-like adhesive may be the same or different from each other. In addition, it is preferable that the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are both smaller than the surface of the layer closer to the substrate side than the intermediate layer and the film-like adhesive (for example, the first surface of the adhesive layer). The area of one side) may be the same or different from each other. In addition, the outer peripheral positions of the intermediate layer and the film-like adhesive may be consistent or not consistent in these radial directions. Next, each layer constituting the semiconductor device manufacturing sheet of this embodiment will be described in more detail.

○Substrate The aforementioned substrate is in the form of a sheet or a film. The constituent materials of the aforementioned substrate are preferably various resins. Specifically, for example, polyethylene (low density polyethylene (LLDPE; linear low density polyethylene), linear low density polyethylene (LLDPE; linear low density polyethylene) ), high-density polyethylene (HDPE, etc.)), polypropylene (PP; polypropylene), polybutene, polybutadiene, polymethylpentene, styrene-ethylene butene-styrene block copolymer, poly Vinyl chloride, vinyl chloride copolymer, polyethylene terephthalate (PET; polyethylene terephthalate), polybutylene terephthalate (PBT; polybutylene terephthalate), polyurethane, polyurethane Ester acrylate, polyimide (PI; polyimide), ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer, and Ethylene copolymers other than ethylene-(meth)acrylate copolymers, polystyrene, polycarbonate, fluororesin, hydrogenated products, modified products, cross-linked products or copolymers of any of these resins, etc.

In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the concept of "(meth)acrylate" includes both "acrylate" and "methacrylate", and the term "(meth)acrylic acid" The concept includes both "acryloyl" and "methacryloyl".

The resin constituting the base material may be only one type or two or more types. In the case of two or more types, the combination and ratio of these resins can be arbitrarily selected.

The substrate may be composed of one layer (single layer), or may be composed of two or more layers. When the substrate is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited within a range that does not impair the efficacy of the present invention. In this specification, it is not limited to the case of the base material. The so-called "plural layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only a part of the layers may be the same." "A plurality of layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other".

The thickness of the substrate can be appropriately selected according to the purpose, preferably 50 μm to 300 μm, and more preferably 60 μm to 150 μm. By making the thickness of the substrate above the aforementioned lower limit, the structure of the substrate can be more stabilized. By making the thickness of the base material below the aforementioned upper limit value, the film-like adhesive can be cut more easily during blade dicing and during the aforementioned expansion of the semiconductor device manufacturing sheet. Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate.

In order to improve the adhesion between the substrate and other layers such as the adhesive layer provided on the substrate, the surface of the substrate can also be embossed by sandblasting, solvent treatment, embossing treatment, etc.; corona discharge treatment , Electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments. The surface of the substrate can also be treated with primer. The substrate may also have: an antistatic coating; when it is overlapped with the sticky wafer, it can prevent the substrate from adhering to other sheets or the substrate from adhering to the layer of the adsorption station.

The base material may contain various well-known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the aforementioned main constituent materials such as resins.

The optical properties of the substrate are not particularly limited within the range that does not impair the efficacy of the present invention. The substrate can also be, for example, a substrate that allows laser light or energy rays to penetrate.

The substrate can be manufactured by a known method. For example, a substrate containing resin (using resin as a constituent material) can be manufactured by molding the aforementioned resin or a resin composition containing the aforementioned resin.

○Adhesive layer The aforementioned adhesive layer may be in the form of a sheet or a film, and contains an adhesive. The adhesive layer can be formed using an adhesive composition containing the aforementioned adhesive. For example, the adhesive composition can be applied to the surface to be formed of the adhesive layer and dried as necessary to form the adhesive layer on the target site.

In the adhesive layer, the ratio of the total content of one or two or more of the following contained components of the adhesive layer to the total mass of the adhesive layer does not exceed 100% by mass. Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the following contained components of the adhesive composition to the total mass of the adhesive composition does not exceed 100% by mass.

The application of the adhesive composition can be performed by a known method, for example, an air knife coater, a knife coater, a bar coater, a gravure coater, a roll coater, and a roll knife can be used. Coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, touch coater, etc.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described later, it is preferable to heat and dry it. In this case, for example, at 70°C to 130°C for 10 seconds to 5 minutes Dry conditions are better.

Examples of the aforementioned adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. It is preferably an acrylic resin.

In addition, in the present invention, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resins include not only resins with adhesive properties, but also resins that exhibit adhesiveness when used in combination with additives and other ingredients, or those that exhibit adhesiveness by the presence of heat or water as a trigger. Resin etc.

The adhesive layer may be either curable or non-curable, for example, it may be either energy-ray curable or non-energy-ray curable. The hardening adhesive layer can easily adjust the physical properties before and after hardening.

In this specification, the so-called "energy line" refers to electromagnetic waves or charged particle beams with energy quantum. Examples of the energy rays include ultraviolet rays, radiation rays, electron beams, and the like. The ultraviolet light can be irradiated by using a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source, for example. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In addition, in the present invention, the term "energy ray curability" means the property of curing by irradiation of energy rays, and the term "non-energy ray curability" means the property of not curing even if energy rays are irradiated.

The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other. These The combination of multiple layers is not particularly limited.

The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm. The "thickness of the adhesive layer" here means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.

The optical properties of the adhesive layer are not particularly limited as long as they are within the range that does not impair the efficacy of the present invention. For example, the adhesive layer can also be one that allows energy rays to penetrate. Next, the aforementioned adhesive composition will be described.

[Adhesive composition] When the adhesive layer is energy-ray-curable, as an adhesive composition containing an energy-ray-curable adhesive, that is, an energy-ray-curable adhesive composition, for example, the following adhesive compositions can be cited: The adhesive composition (I-1) contains a non-energy-ray curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)") and an energy-ray curable compound; Adhesive composition (I-2), contained in the side chain of non-energy-ray-curable adhesive resin (I-1a) with unsaturated group introduced into the side chain of energy-ray-curable adhesive resin (I-2a) (below , Sometimes abbreviated as "adhesive resin (I-2a)"); adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

[Adhesive composition (I-1)] The aforementioned adhesive composition (I-1) contains a non-energy ray curable adhesive resin (I-1a) and an energy ray curable compound as described above.

[Adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably acrylic resin. As said acrylic resin, the acrylic polymer which has at least the structural unit derived from the alkyl (meth)acrylate is mentioned, for example. The structural unit possessed by the aforementioned acrylic resin may be only one type or two or more types. In the case of two or more types, the combination and ratio of these structural units can be arbitrarily selected.

Adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination of adhesive resin (I-1a) and The ratio can be chosen arbitrarily.

In the adhesive composition (I-1), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-1) is preferably 5 to 99% by mass, and 10% by mass % To 95% by mass is more preferable, and 15% to 90% by mass is particularly preferable.

[Energy ray hardening compound] Examples of the aforementioned energy ray curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have energy ray polymerizable unsaturated groups and can be cured by energy ray irradiation. Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (Meth)acrylate such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.; (meth)acrylate aminomethyl Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above. In terms of relatively large molecular weight and difficult to reduce the storage elastic modulus of the adhesive layer, the energy ray curable compound is preferably (meth)acrylate urethane, (meth)acrylate urethane formic acid Ester oligomers.

The aforementioned energy ray curable compound contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these energy ray curable compounds may be Free to choose.

In the adhesive composition (I-1), the ratio of the content of the aforementioned energy ray curable compound to the total mass of the adhesive composition (I-1) is preferably 1% to 95% by mass, preferably 5% by mass It is more preferably from 90% by mass, and particularly preferably from 10% by mass to 85% by mass.

[Crosslinking agent] When the aforementioned acrylic polymer used in the adhesive resin (I-1a) has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the alkyl (meth)acrylate, the adhesive The composition (I-1) preferably further contains a crosslinking agent.

The aforementioned crosslinking agent reacts with the aforementioned functional group, for example, to crosslink the adhesive resins (I-1a) with each other. Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy crosslinking agents such as ethylene glycol glycidyl ether (crosslinking agents with glycidyl groups); aziridines such as hexa[1-(2-methyl)-aziridinyl] triphosphoryl triazine Crosslinking agent (crosslinking agent with aziridin group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate crosslinking agent Agent (crosslinking agent with isocyanuric acid skeleton) and so on. The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of improving the cohesive force of the adhesive and improving the adhesive force of the adhesive layer, and ease of availability.

The crosslinking agent contained in the adhesive composition (I-1) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these crosslinking agents can be arbitrarily selected.

In the case of using a cross-linking agent, in the aforementioned adhesive composition (I-1), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a), It is more preferably from 0.1 parts by mass to 20 parts by mass, and particularly preferably from 0.3 parts by mass to 15 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. Even if the adhesive composition (I-1) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

Examples of the aforementioned photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds; benzyl Thioether compounds such as phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetin; benzil; benzil; benzophenone; 2,4-diethylthioxanthone ; 1,2-Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone and the like. In addition, as the aforementioned photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type or two or more types. When there are two or more types, the combination and ratio of these photopolymerization initiators can be arbitrary choose.

In the case of using a photopolymerization initiator, in the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to the content of the aforementioned energy ray curable compound 100 parts by mass , More preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives] The adhesive composition (I-1) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, Known additives such as reaction delay agents and crosslinking accelerators (catalysts).

The so-called reaction delay agent, for example, refers to the effect of the catalyst mixed into the adhesive composition (I-1), which causes unexpected interaction in the adhesive composition (I-1) during storage. The components of the joint reaction. As the reaction delay agent, for example, a compound that forms a chelate complex by a chelate against a catalyst can be cited, and more specifically, a compound having two or more carbonyl groups (-C(= O)-) Compounds.

The other additives contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these other additives can be arbitrarily selected.

The content of other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected according to the type of the other additives.

[Solvent] The adhesive composition (I-1) may also contain a solvent. By containing a solvent, the adhesive composition (I-1) can improve the applicability to the surface to be coated.

The aforementioned solvent is preferably an organic solvent.

[Adhesive composition (I-2)] The aforementioned adhesive composition (I-2) is contained in the side chain of the non-energy-ray-curable adhesive resin (I-1a) as described above. ).

[Adhesive resin (I-2a)] The aforementioned adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy-ray polymerizable unsaturated group.

The aforementioned unsaturated group-containing compound is a compound having the following group: in addition to the aforementioned energy-ray polymerizable unsaturated group, it also has adhesiveness by reacting with the functional group in the adhesive resin (I-1a) Resin (I-1a) is the bonding base. Examples of the energy ray polymerizable unsaturated group include: (meth)acrylic acid group, vinyl group (ethylene group), allyl group (2-propenyl group), etc., preferably (meth)acrylic acid group base. Examples of groups that can be bonded to the functional groups in the adhesive resin (I-1a) include: isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amino groups, and carboxyl groups or epoxy groups that can be bonded The hydroxyl and amino groups, etc.

Examples of the aforementioned unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, and the like.

Adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, these adhesive resins (I-2a) The combination and ratio of can be chosen arbitrarily.

In the adhesive composition (I-2), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-2) is preferably 5 to 99% by mass, and 10 Mass% to 95% by mass is more preferable, and 10% by mass to 90% by mass is particularly preferable.

[Crosslinking agent] Adhesive resin (I-2a), for example, as in adhesive resin (I-1a), when the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer is used, the adhesive composition (I -2) You may further contain a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-2) include the same crosslinking agent as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-2) may be only one type or two or more types. When there are two or more types, the combination and ratio of these crosslinking agents can be arbitrarily selected.

In the case of using a cross-linking agent, in the aforementioned adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). It is more preferably from 0.1 parts by mass to 20 parts by mass, and particularly preferably from 0.3 parts by mass to 15 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator can fully undergo a curing reaction even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays.

The aforementioned photopolymerization initiator in the adhesive composition (I-2) may include the same photopolymerization initiator as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators can be arbitrarily selected .

In the case of using a photopolymerization initiator, in the adhesive composition (I-2), the content of the photopolymerization initiator is 0.01 to 20 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a) Preferably, it is more preferably from 0.03 parts by mass to 10 parts by mass, particularly preferably from 0.05 parts by mass to 5 parts by mass.

[Other additives, solvents] The adhesive composition (I-2) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the efficacy of the present invention. In addition, the adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-2), those that are the same as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these other additives and the solvent can be arbitrarily selected. The content of other additives and solvents in the adhesive composition (I-2) is not particularly limited, as long as they are appropriately selected according to the kind.

[Adhesive composition (I-3)] The adhesive composition (I-3) contains the adhesive resin (I-2a) and the energy ray curable compound as described above.

In the adhesive composition (I-3), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-3) is preferably 5 to 99% by mass, and 10 Mass% to 95% by mass is more preferred, and 15% to 90% by mass is particularly preferred.

[Energy ray hardening compound] Examples of the aforementioned energy-ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy-ray polymerizable unsaturated group and can be cured by irradiation with energy rays, including The same compound as the energy ray curable compound contained in the adhesive composition (I-1). The aforementioned energy ray curable compound contained in the adhesive composition (I-3) may be only one type or two or more types. When there are two or more types, the combination and ratio of these energy ray curable compounds can be arbitrary choose.

In the aforementioned adhesive composition (I-3), the content of the aforementioned energy ray curable compound relative to 100 parts by mass of the adhesive resin (I-2a) is preferably 0.01 to 300 parts by mass, preferably 0.03 parts by mass It is more preferably to 200 parts by mass, particularly preferably from 0.05 to 100 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator can fully undergo a curing reaction even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays.

The aforementioned photopolymerization initiator in the adhesive composition (I-3) may include the same photopolymerization initiator as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators can be arbitrarily selected .

In the case of using a photopolymerization initiator, the content of the photopolymerization initiator in the adhesive composition (I-3) is relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray curable compound It is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, and particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives, solvents] The adhesive composition (I-3) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the efficacy of the present invention. In addition, the adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-3), those that are the same as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these other additives and the solvent can be arbitrarily selected. The content of other additives and solvents in the adhesive composition (I-3) is not particularly limited, as long as they are appropriately selected according to the kind.

[Adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3)] The adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) have been mainly explained so far, but the ingredients explained as the contained ingredients may also be The same applies to all adhesive compositions other than these three adhesive compositions (in this specification, referred to as "adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3))物").

As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy-ray-curable adhesive composition, non-energy-ray-curable adhesives can also be cited Composition. Examples of non-energy-ray curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and esters. The adhesive composition (I-4) of a non-energy-ray-curable adhesive resin (I-1a) such as resin preferably contains an acrylic resin.

Adhesive compositions other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contain one or more crosslinking agents, and the content of the crosslinking agent can be set to The adhesive composition (I-1) mentioned above is the same.

[Adhesive composition (I-4)] As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include those that are the same as the adhesive resin (I-1a) in the adhesive composition (I-1). The adhesive composition (I-4) contains only one type of adhesive resin (I-1a) or two or more types. In the case of two or more types, these adhesive resins (I-1a) The combination and ratio can be selected arbitrarily.

In the adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-4) is preferably 5 to 99% by mass, and 10 Mass% to 95% by mass is more preferred, and 15% to 90% by mass is particularly preferred.

[Crosslinking agent] When using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a), The adhesive composition (I-4) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-4) include the same crosslinking agent as the crosslinking agent in the adhesive composition (I-1). The cross-linking agent contained in the adhesive composition (I-4) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these cross-linking agents can be arbitrarily selected.

In the aforementioned adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a) Parts are more preferable, and 0.1 parts by mass to 10 parts by mass are particularly preferable.

[Other additives, solvents] The adhesive composition (I-4) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the efficacy of the present invention. In addition, the adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-4), those that are the same as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-4) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these other additives and the solvent can be arbitrarily selected. The content of other additives and solvents in the adhesive composition (I-4) is not particularly limited, as long as they are appropriately selected according to the type.

[Manufacturing method of adhesive composition] Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4) and other adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition other than that can be obtained by blending the aforementioned adhesive and components other than the aforementioned adhesive if necessary to form the adhesive composition. The order of addition when preparing each component is not particularly limited, and two or more components may be added at the same time. When using a solvent, you can mix the solvent with any compounding component other than the solvent and dilute the compounding component in advance for use, or use the solvent and these compounding components without pre-diluting any compounding component other than the solvent. Mix to use. The method of mixing each component during compounding is not particularly limited, and it can be appropriately selected from the following known methods: a method of rotating a stirrer or a stirring blade, etc. for mixing; a method of mixing using a mixer; applying ultrasonic waves Methods of mixing, etc. Regarding the temperature and time when each component is added and mixed, as long as it does not deteriorate each compounding component, it is not particularly limited and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

○Composition for forming intermediate layer and intermediate layer The intermediate layer is in the form of a sheet or a film, and contains the non-silicone resin as a main component. The intermediate layer may contain only non-silicon-based resins (composed of non-silicon-based resins), or may contain non-silicon-based resins and components other than non-silicon-based resins.

The intermediate layer can be formed using, for example, a composition for forming an intermediate layer containing the aforementioned non-silicon-based resin. For example, the intermediate layer may be formed by applying the aforementioned composition for forming the intermediate layer on the surface to be formed on the intermediate layer, and drying it as necessary to form the target portion.

In the intermediate layer, the ratio of the total content of one or two or more of the following contained components in the intermediate layer to the total mass of the intermediate layer does not exceed 100% by mass. Similarly, in the composition for forming the intermediate layer, the ratio of the total content of one or two or more of the composition for forming the intermediate layer to the total mass of the composition for forming the intermediate layer to the total mass of the composition for forming the intermediate layer shall not exceed 100% by mass .

The application of the composition for forming an intermediate layer can be performed in the same manner as the application of the above-mentioned adhesive composition.

The drying conditions of the composition for forming an intermediate layer are not particularly limited. When the composition for forming an intermediate layer contains a solvent described later, it is preferable to heat and dry it. In this case, it is preferable to dry it at 60°C to 130°C for 1 minute to 6 minutes.

The weight average molecular weight of the aforementioned non-silicone resin is 100,000 or less. Based on the viewpoint of improving the division suitability of the semiconductor wafer of the semiconductor device manufacturing sheet, the weight average molecular weight of the non-silicon resin may be any of 80,000 or less, 60,000 or less, and 40,000 or less, for example.

The lower limit of the weight average molecular weight of the aforementioned non-silicone resin is not particularly limited. For example, the aforementioned non-silicone resin with a weight average molecular weight of 5000 or more is easier to obtain.

The weight average molecular weight of the aforementioned non-silicone resin can be appropriately adjusted within a range set by combining the above-mentioned lower limit and any upper limit arbitrarily. For example, in one embodiment, the aforementioned weight average molecular weight may be any of 5000 to 100,000, 5,000 to 80,000, 5,000 to 60,000, and 5,000 to 40,000.

In this embodiment, the phrase "the intermediate layer contains a non-silicone resin with a weight average molecular weight of 100,000 or less as the main component" means that "the intermediate layer can fully function by containing a non-silicon resin with a weight average molecular weight of 100,000 or less. The aforementioned non-silicone resin is contained in an amount to achieve the effect." From this point of view, the ratio of the content of the aforementioned non-silicon-based resin to the total mass of the intermediate layer in the intermediate layer (in other words, the content of the aforementioned non-silicon-based resin in the composition for forming the intermediate layer relative to all components other than the solvent The ratio of the total content) is preferably 80% by mass or more, and more preferably 90% by mass or more. For example, it can be any of 95% by mass or more, 97% by mass or more, and 99% by mass or more. On the other hand, the aforementioned ratio is 100% by mass or less.

The aforementioned non-silicon resin having a weight average molecular weight of 100,000 or less is not particularly limited as long as it does not contain silicon atoms as constituent atoms and is a resin component with a weight average molecular weight of 100,000 or less. The aforementioned non-silicon resin may be, for example, any of a polar resin having a polar group and a non-polar resin having no polar group. For example, the aforementioned non-silicon-based resin has high solubility in the aforementioned intermediate layer forming composition, and the aforementioned intermediate layer forming composition has higher coating suitability, and a polar resin is preferred.

Unless otherwise limited in this specification, the term "non-silicone resin" means the non-silicone resin having the above-mentioned weight average molecular weight of 100,000 or less.

The aforementioned non-silicon resin may be, for example, a homopolymer of a polymer of one monomer (in other words, having only one structural unit), or a polymer of two or more monomers (in other words, having two or more structural units). ) The copolymer.

Examples of the aforementioned polar group include a carbonyloxy group (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), and the like.

The aforementioned polar resin may have only a structural unit with a polar group, or may have both a structural unit with a polar group and a structural unit without a polar group.

Examples of the aforementioned structural unit having a polar group include structural units derived from vinyl acetate. As the aforementioned structural unit having no polar group, for example, a structural unit derived from ethylene and the like can be given.

In the aforementioned polar resin, the ratio of the mass of the constituent unit having a polar group to the total mass of all constituent units is preferably 5 mass% to 70 mass%, for example, 7.5% to 55% by mass, and 10 mass% to 10% by mass. Any one of 40% by mass. In other words, in the aforementioned polar resin, the ratio of the mass of the constituent units without polar groups to the total mass of all constituent units is preferably 30% to 95% by mass, for example, 45% to 92.5% by mass, and 60% by mass Any one of% to 90% by mass. By making the mass ratio of the constituent units with polar groups above the aforementioned lower limit, the characteristics of the aforementioned polar resins due to the polar groups will be more remarkable. By making the ratio of the mass of the constituent units with polar groups below the aforementioned upper limit, the aforementioned polar resin can more moderately have the characteristics produced by the absence of polar groups.

Examples of the aforementioned polar resin include ethylene-vinyl acetate copolymers and the like. Among them, preferred polar resins include, for example, the ratio of the mass of the constituent units derived from vinyl acetate to the total mass of all constituent units in the ethylene-vinyl acetate copolymer (sometimes referred to in this specification as "The content of the constituent unit derived from vinyl acetate") is a polar resin of 10% to 40% by mass. In other words, as a preferred polar resin, for example, in an ethylene-vinyl acetate copolymer, the ratio of the mass of the constituent units derived from ethylene to the total mass of all constituent units is 60% to 90% by mass. Polar resin.

Examples of the aforementioned non-polar resin include low density polyethylene (LLDPE; linear low density polyethylene), linear low density polyethylene (LLDPE; linear low density polyethylene), and metallocene catalyst linear low density polyethylene ( Metallocene LLDPE), medium density polyethylene (MDPE; medium density polyethylene), high density polyethylene (HDPE; high density polyethylene) and other polyethylene (PE; polyethylene); polypropylene (PP; polypropylene), etc.

The composition for forming the intermediate layer and the aforementioned non-silicone resin contained in the intermediate layer may be one type or two or more types. In the case of two or more types, the combination and ratio of these non-silicone resins can be arbitrarily selected. For example, the composition for forming the intermediate layer and the intermediate layer may contain one or more types of non-silicon resins as polar resins and no non-silicon resins that are not polar resins, and may contain one or more types of non-silicon resins. Two or more kinds of non-silicon resins that are not polar resins and do not contain non-silicon resins that are polar resins. Both non-silicon resins that are polar resins and non-silicon resins that are not polar resins contain one or It is more than two kinds. The composition for forming the intermediate layer and the intermediate layer preferably contain at least a non-silicon resin as a polar resin.

In the composition for forming the intermediate layer and the intermediate layer, the ratio of the content of the aforementioned non-silicone resin as a polar resin to the total content of the aforementioned non-silicone resin is preferably 80% by mass or more, more preferably 90% by mass or more For example, it may be any of 95% by mass or more, 97% by mass or more, and 99% by mass or more. By making the aforementioned ratio above the aforementioned lower limit, the effect of using the aforementioned polar resin can be obtained more significantly. On the other hand, the aforementioned ratio is 100% by mass or less.

That is, in the composition for forming the intermediate layer and the intermediate layer, the ratio of the content of the non-silicon resin as the non-polar resin to the total content of the non-silicon resin is preferably 20% by mass or less, and 10% by mass The following is more preferable, and for example, it may be any of 5% by mass or less, 3% by mass or less, and 1% by mass or less. On the other hand, the aforementioned ratio is 0% by mass or more.

Based on the viewpoint of good workability, the composition for forming the intermediate layer preferably contains a solvent in addition to the aforementioned non-silicon-based resin, and may also contain components that are not equivalent to any of the aforementioned non-silicon-based resin and solvent (in this specification) Sometimes called "additives"). The intermediate layer may contain only the aforementioned non-silicone resin, or both the aforementioned non-silicone resin and the aforementioned additives.

The aforementioned additives may be any of a resin component (sometimes referred to as "other resin component" in this specification) and a non-resin component.

Examples of the aforementioned other resin components include non-silicon resins and silicone resins having a weight average molecular weight (Mw) exceeding 100,000 (Mw) 100,000).

The non-silicon resin having a weight average molecular weight of more than 100,000 is not particularly limited as long as it satisfies such conditions.

The intermediate layer containing the aforementioned silicon-based resin, as described later, can make the pickup of the semiconductor wafer with the film-like adhesive easier.

The aforementioned silicon-based resin is not particularly limited as long as it is a resin component having silicon atoms as constituent atoms. For example, the weight average molecular weight of the silicone resin is not particularly limited.

As a preferable silicon-based resin, for example, a resin component that exhibits a release effect on the adhesive component, and a silicone-based resin (resin component with a silicone bond (-Si-O-Si-), also called It is more preferably a siloxane compound).

As said silicone resin, polydialkylsiloxane etc. are mentioned, for example. The carbon number of the alkyl group of the aforementioned polydialkylsiloxane is preferably 1-20. In the aforementioned polydialkylsiloxane, the two alkyl groups bonded to one silicon atom may be the same or different from each other. When the two alkyl groups bonded to one silicon atom are different from each other, the combination of these two alkyl groups is not particularly limited. As said polydialkylsiloxane, polydimethylsiloxane etc. are mentioned.

The aforementioned non-resin component may be any one of an organic compound and an inorganic compound, for example, and is not particularly limited.

The composition for forming the intermediate layer and the aforementioned additives contained in the intermediate layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these additives can be arbitrarily selected. For example, the composition for forming the intermediate layer and the intermediate layer, as the aforementioned additives, may contain one or two or more resin components without non-resin components, and may contain one or two or more non-resin components It does not contain a resin component, and may contain one or two or more of both the resin component and the non-resin component.

When the composition for forming the intermediate layer and the intermediate layer contain the aforementioned additives, the ratio of the content of the aforementioned non-silicon-based resin to the total mass of the intermediate layer in the intermediate layer (in other words, in the composition for forming the intermediate layer, the aforementioned non-silicon The ratio of the content of the resin to the total content of all components other than the solvent is preferably 90% to 99.99% by mass, for example, 90% to 97.5% by mass, 90% to 95% by mass, and 90% by mass Any one of% to 92.5% by mass may be any of 92.5% to 99.99% by mass, 95% to 99.99% by mass, and 97.5% to 99.99% by mass, and may be 92.5% to 97.5% by mass . When the composition for forming the intermediate layer and the intermediate layer contain the aforementioned additives, the ratio of the content of the aforementioned additives in the intermediate layer to the total mass of the intermediate layer (in other words, in the composition for forming the intermediate layer, the content of the aforementioned additives relative to the total mass of the intermediate layer The ratio of the total content of all components other than the solvent) is preferably 0.01% by mass to 10% by mass, for example, it can be 2.5% by mass to 10% by mass, 5% by mass to 10% by mass, and 7.5% by mass to 10% by mass. Any one may be 0.01% to 7.5% by mass, 0.01% to 5% by mass, and 0.01% to 2.5% by mass, and may be 2.5% to 7.5% by mass.

The aforementioned solvent contained in the composition for forming an intermediate layer is not particularly limited, but preferable examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane- 1-alcohol), 1-butanol and other alcohols; ethyl acetate and other esters; acetone, methyl ethyl ketone and other ketones; tetrahydrofuran and other ethers; dimethylformamide, N-methylpyrrolidone and other amides ( Compounds with amide bond) and so on. The solvent contained in the composition for forming an intermediate layer may be only one type or two or more types, and when there are two or more types, the combination and ratio of these solvents can be arbitrarily selected.

The solvent contained in the composition for forming an intermediate layer is preferably tetrahydrofuran or the like from the viewpoint that the components contained in the composition for forming an intermediate layer can be mixed more uniformly.

The content of the solvent in the composition for forming an intermediate layer is not particularly limited, as long as it is appropriately selected in accordance with the types of components other than the solvent, for example.

As described later, based on the viewpoint that semiconductor wafers with film-like adhesives can be picked up more easily, a preferable intermediate layer includes, for example, an ethylene-vinyl acetate copolymer containing as the aforementioned non-silicon-based resin and silicon as the aforementioned additive. Oxane compound, the ratio of the content of the aforementioned ethylene-vinyl acetate copolymer (the aforementioned non-silicon resin) in the intermediate layer to the total mass of the intermediate layer is in any of the above numerical ranges, and the aforementioned silicone in the intermediate layer The ratio of the content of the compound (the aforementioned additives) to the total mass of the intermediate layer falls within any of the above numerical ranges. For example, such an intermediate layer includes an ethylene-vinyl acetate copolymer as the aforementioned non-silicon resin and a silicone compound as the aforementioned additive, and the aforementioned ethylene-vinyl acetate copolymer in the intermediate layer The ratio of the content to the total mass of the intermediate layer is 90% to 99.99% by mass, and the ratio of the content of the aforementioned silicone compound in the intermediate layer to the total mass of the intermediate layer is 0.01% to 10% by mass. However, this is an example of a preferable intermediate layer.

As a more preferable intermediate layer, for example, the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon resin and a silicone compound as the additive. In the ethylene-vinyl acetate copolymer, acetic acid The ratio of the mass of the constituent units derived from vinyl ester to the total mass of all constituent units (in other words, the content of the constituent units derived from vinyl acetate) is 10% to 40% by mass. In the intermediate layer, the ethylene -The ratio of the content of the vinyl acetate copolymer to the total mass of the intermediate layer is 90% to 99.99% by mass, and the ratio of the content of the silicone compound in the intermediate layer to the total mass of the intermediate layer is 0.01 Mass% to 10% by mass. However, this is an example of a better intermediate layer.

In the semiconductor device manufacturing sheet, the film-like adhesive side surface of the intermediate layer (for example, the first surface 13a of the intermediate layer 13 shown in FIG. 1) is subjected to X-ray Photoelectron Spectroscopy (X-ray Photoelectron Spectroscopy, this (Sometimes referred to as "XPS" in the manual) In the analysis, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon (sometimes abbreviated as "the ratio of silicon concentration" in this manual) is based on the amount of element It is better to use 1% to 20% on ear basis. By using a semiconductor device manufacturing sheet provided with such an intermediate layer, as described later, it is easier to pick up a semiconductor wafer with a film-like adhesive.

XPS analysis can set the analysis object to the side of the film-like adhesive of the intermediate layer, use an X-ray photoelectron spectroscopic analysis device, set the X-ray irradiation angle to 45°, set the X-ray beam diameter to 20μmφ, and set the output Set it to 4.5W.

The ratio of the aforementioned silicon concentration can be calculated by the following formula. [Measured value of silicon concentration in XPS analysis (atomic%)]/{[Measured value of carbon concentration in XPS analysis (atomic%)] + [Measured value of oxygen concentration in XPS analysis (atomic%)] + [ Measurement value of nitrogen concentration in XPS analysis (atomic%)] + [Measurement value of silicon concentration in XPS analysis (atomic%)]}×100

Based on the view that this effect is more significant, the ratio of the aforementioned silicon concentration can be any of 4% to 20%, 8% to 20%, and 12% to 20%, for example, based on the molar basis of the element, which can be 1 Any of% to 16%, 1% to 12%, and 1% to 8% may be any of 4% to 16%, and 8% to 12%.

When the XPS analysis is performed as described above, it is possible to detect other elements that are not equivalent to any of carbon, oxygen, nitrogen, and silicon in the aforementioned surface of the intermediate layer (the surface to be analyzed by XPS). However, usually even if the aforementioned other elements are detected, the concentration is very small. When calculating the ratio of the aforementioned silicon concentration, the ratio of the aforementioned silicon concentration can be calculated with high accuracy by using only the measured values of the concentration of carbon, oxygen, nitrogen, and silicon.

The intermediate layer can be composed of one layer (single layer) or two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other. The combination of these multiple layers is not particularly limited. .

As mentioned above, the maximum value of the width of the intermediate layer is preferably smaller than the maximum value of the width of the adhesive layer and the maximum value of the width of the substrate. The maximum width of the intermediate layer can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the intermediate layer can be 150 mm to 160 mm, 200 mm to 210 mm, or 300 mm to 310 mm. These three numerical ranges correspond to a semiconductor wafer with a maximum width of 150mm, a semiconductor wafer of 200mm, or a semiconductor wafer of 300mm in the direction parallel to the attachment surface of the semiconductor device manufacturing sheet. However, as described above, after dicing is accompanied by the formation of the modified layer of the semiconductor wafer, the film-like adhesive is cut by expanding the semiconductor device manufacturing sheet. As will be described later, most of the diced semiconductor A wafer (semiconductor wafer group) is regarded as a whole, and a semiconductor device manufacturing sheet is attached to these semiconductor wafers.

Unless otherwise limited in this specification, the "width of the intermediate layer" means, for example, the "width of the intermediate layer in a direction parallel to the first surface of the intermediate layer". For example, when the planar shape is a circular intermediate layer, the maximum value of the width of the aforementioned intermediate layer becomes the circle diameter of the aforementioned planar shape. The same applies to semiconductor wafers. That is, the so-called "width of the semiconductor wafer" means "the width of the semiconductor wafer in the direction parallel to the attachment surface of the semiconductor device manufacturing sheet". For example, in the case of a semiconductor wafer whose planar shape is a circular shape, the maximum value of the width of the aforementioned semiconductor wafer becomes the circular diameter of the aforementioned planar shape.

The maximum value of the width of the intermediate layer of 150 mm to 160 mm means that the maximum value of the width of the semiconductor wafer of 150 mm is equal to or less than 10 mm. Similarly, the maximum width of the intermediate layer from 200 mm to 210 mm means that the maximum width of the semiconductor wafer is equal to or less than 10 mm relative to 200 mm. Similarly, the maximum value of the width of the intermediate layer from 300 mm to 310 mm means that the maximum value of the width of the semiconductor wafer is equal to or less than 10 mm relative to 300 mm. That is, in this embodiment, regardless of whether the maximum width of the semiconductor wafer is 150 mm, 200 mm, or 300 mm, the difference between the maximum width of the intermediate layer and the maximum width of the semiconductor wafer may be, for example, 0 mm To 10mm.

The thickness of the intermediate layer can be appropriately selected according to the purpose, preferably 5 μm to 150 μm, more preferably 5 μm to 120 μm, for example, it can be any of 10 μm to 90 μm and 10 μm to 60 μm, and can be 30 μm to 120 μm and 60 μm to 120 μm. Any of them. By making the thickness of the intermediate layer more than the aforementioned lower limit, the structure of the intermediate layer can be more stabilized. By making the thickness of the intermediate layer below the aforementioned upper limit value, the film-like adhesive can be cut more easily during blade dicing and during the aforementioned expansion of the semiconductor device manufacturing sheet. The "thickness of the intermediate layer" here means the thickness of the entire intermediate layer. For example, the thickness of the intermediate layer composed of a plurality of layers means the total thickness of all the layers constituting the intermediate layer.

When the intermediate layer contains the aforementioned silicone resin, especially when the compatibility between the silicone resin and the aforementioned non-silicon resin as the main component is low, the silicon resin in the intermediate layer tends to concentrate in the semiconductor device manufacturing sheet It exists in the vicinity of both sides of the intermediate layer (the first surface and the opposite side). In addition, the stronger this tendency is, the easier the film-like adhesive adjacent to (directly in contact with) the intermediate layer will be peeled from the intermediate layer. As described later, the semiconductor wafer with the film-like adhesive can be picked up more easily. For example, compare the case of intermediate layers that are different from each other only in thickness, but are the same as each other in terms of composition, the area of the two surfaces, and other thicknesses. In these intermediate layers, the content of the silicone resin is relative to the total mass of the intermediate layer. The ratios (% by mass) are the same as each other. However, the content (parts by mass) of the silicone resin in the intermediate layer is much higher for the thicker intermediate layer than the thinner intermediate layer. Therefore, when the silicon-based resin is easily concentrated in the intermediate layer as described above, the thicker intermediate layer is compared to the thinner intermediate layer, and the silicon-based resin concentrates on both sides (the first surface and the opposite side)之面) and nearby areas will increase. Therefore, even if the aforementioned ratio is not changed, by adjusting the thickness of the intermediate layer in the semiconductor device manufacturing sheet, the pick-up suitability of the semiconductor chip with the film-like adhesive can be adjusted. For example, by increasing the thickness of the intermediate layer in the semiconductor device manufacturing sheet, it is easier to pick up the semiconductor wafer with the film-like adhesive.

○Film adhesive The aforementioned film-like adhesive has curability, preferably has thermosetting properties, and preferably has pressure-sensitive adhesive properties. The film-like adhesive, which has both thermosetting and pressure-sensitive adhesive properties, can be attached by lightly pressing against various adherends in the uncured state. In addition, the film-like adhesive may be one that can be softened by heating and attached to various adherends. The film-like adhesive finally becomes a cured product with high impact resistance through curing. This cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

When the semiconductor device manufacturing sheet is viewed from above, the area of the film adhesive (that is, the area of the first surface) is set to be smaller than the area of the substrate (that is, the area of the first surface) so as to be close to the area of the semiconductor wafer before division. The area of one side) and the area of the adhesive layer (that is, the area of the first side) are better. In such a sheet for manufacturing a semiconductor device, a portion of the first surface of the adhesive layer has a region that is not in contact with the intermediate layer and the film-like adhesive (that is, the aforementioned non-layered region). Thereby, the expansion of the semiconductor device manufacturing sheet becomes easier, and the force applied to the film-like adhesive during expansion is not dispersed, and the film-like adhesive can be cut more easily.

The film adhesive can be formed using an adhesive composition containing constituent materials of the film adhesive. For example, by coating the adhesive composition on the surface to be formed of the film-like adhesive, and drying it as necessary, the film-like adhesive can be formed on the target site.

In the film adhesive, the ratio of the total content of one or two or more of the following contained components of the film adhesive to the total mass of the film adhesive does not exceed 100% by mass. Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the following contained components of the adhesive composition to the total mass of the adhesive composition does not exceed 100% by mass.

The application of the adhesive composition can be carried out in the same manner as in the case of the above-mentioned application of the adhesive composition.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described later, it is better to heat and dry it. In this case, it is better to dry it under the conditions of, for example, 70°C to 130°C for 10 seconds to 5 minutes.

The film adhesive can be composed of one layer (single layer) or two or more layers. When it is composed of multiple layers, these multiple layers can be the same or different from each other. There is no combination of these multiple layers. Specially limited.

As mentioned above, the maximum width of the film adhesive is preferably smaller than the maximum width of the adhesive layer and the maximum width of the substrate. The maximum width of the film adhesive relative to the size of the semiconductor wafer can also be the same as the maximum width of the intermediate layer described previously. That is, the maximum width of the film adhesive can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the film adhesive can be 150 mm to 160 mm, 200 mm to 210 mm, or 300 mm to 310 mm. These three numerical ranges correspond to a semiconductor wafer with a maximum width of 150mm, a semiconductor wafer of 200mm, or a semiconductor wafer of 300mm in the direction parallel to the attachment surface of the semiconductor device manufacturing sheet.

Unless otherwise limited in this specification, the "width of the film-like adhesive" means, for example, "the width of the film-like adhesive in a direction parallel to the first surface of the film-like adhesive". For example, in the case of a film adhesive whose planar shape is a circular shape, the maximum width of the film adhesive becomes the diameter of the circle of the planar shape. In addition, if not particularly limited, the "width of the film-like adhesive" does not mean the width of the film-like adhesive after cutting during the manufacturing process of the semiconductor wafer with the film-like adhesive described later, but means "cutting The width of the front (uncut) film adhesive".

The maximum width of a film adhesive of 150mm to 160mm is equal to or less than 10mm with respect to the maximum width of a semiconductor wafer of 150mm. Similarly, the maximum width of a film-like adhesive from 200 mm to 210 mm is the same as or less than 10 mm relative to the maximum width of a semiconductor wafer of 200 mm. Similarly, the maximum width of the film adhesive from 300 mm to 310 mm is equal to or less than 10 mm relative to the maximum width of the semiconductor wafer of 300 mm. That is, in this embodiment, the difference between the maximum width of the film adhesive and the maximum width of the semiconductor wafer regardless of whether the maximum width of the semiconductor wafer is 150mm, 200mm, or 300mm, for example It can be 0mm to 10mm.

In this embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film adhesive are both in any of the above numerical ranges. That is, as an example of the semiconductor device manufacturing sheet of this embodiment, the maximum width of the intermediate layer and the maximum width of the film adhesive are both 150mm to 160mm, 200mm to 210mm, or 300mm to 310mm.

The thickness of the film adhesive is not particularly limited, and is preferably 1 μm to 30 μm, more preferably 2 μm to 20 μm, and particularly preferably 3 μm to 10 μm. By making the thickness of the film-like adhesive more than the aforementioned lower limit, higher adhesive force can be obtained with respect to the adherend (semiconductor wafer). By making the thickness of the film-like adhesive to be less than the aforementioned upper limit value, the film-like adhesive can be more easily cut at the time of blade dicing and the aforementioned expansion of the semiconductor device manufacturing sheet. The "thickness of the film adhesive" here means the thickness of the entire film adhesive. For example, the thickness of the film adhesive composed of a plurality of layers means the total thickness of all the layers constituting the film adhesive. Next, the aforementioned adhesive composition will be described.

[Adhesive composition] As a preferable adhesive composition, for example, one containing a polymer component (a) and a thermosetting component (b) can be mentioned. Hereinafter, each component will be explained. In addition, the adhesive composition shown below is a preferable example, and the adhesive composition in this embodiment is not limited to the one shown below.

[Polymer component (a)] The polymer component (a) can be regarded as a component formed by the polymerization reaction of a polymerizable compound, which imparts film-forming properties, flexibility, etc. to the film-like adhesive and improves the adhesiveness (in other words, the adhesive Attachment) of the polymer compound. The polymer component (a) has thermoplasticity but does not have thermosetting properties. The polymer compound in this specification also includes the product of the polycondensation reaction.

The polymer component (a) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these polymer components (a) may be Free to choose.

Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, and the like. Among them, the polymer component (a) is preferably acrylic resin.

In the adhesive composition, the ratio of the content of the polymer component (a) to the total content of all components other than the solvent (that is, the content of the polymer component (a) relative to the film adhesive in the film adhesive The ratio of the total mass) is preferably from 20% by mass to 75% by mass, and more preferably from 30% by mass to 65% by mass.

[Thermosetting component (b)] The thermosetting component (b) is a component having thermosetting properties for thermally curing the film-like adhesive. The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination of these thermosetting components (b) and The ratio can be chosen arbitrarily.

Examples of the thermosetting component (b) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins. Among them, the thermosetting component (b) is preferably an epoxy-based thermosetting resin.

〇Epoxy-based thermosetting resin The epoxy-based thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b2). The epoxy-based thermosetting resin contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination of these epoxy-based thermosetting resins and The ratio can be chosen arbitrarily.

・Epoxy resin (b1) As the epoxy resin (b1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, ortho-cresol novolac epoxy Resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins and other epoxy resins with more than two functions Compound.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film adhesive can be improved.

The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these epoxy resins (b1) may be Free to choose.

・Thermal hardener (b2) The thermal hardener (b2) functions as a hardener for the epoxy resin (b1). As a thermosetting agent (b2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by an anhydride of an acid group, etc. are mentioned, preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride The formed group is more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (b2), examples of phenolic curing agents having phenolic hydroxyl groups include: polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. Phenolic resin, etc. Among the thermosetting agents (b2), examples of the amine curing agent having an amine group include dicyandiamide (DICY).

The thermosetting agent (b2) may have an unsaturated hydrocarbon group.

The thermosetting agent (b2) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these thermosetting agents (b2) can be Free to choose.

In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) relative to 100 parts by mass of the epoxy resin (b1), preferably 0.1 to 500 parts by mass, preferably 1 to 200 parts by mass The part by mass is more preferable, and for example, it may be any one of 1 part by mass to 100 parts by mass, 1 part by mass to 50 parts by mass, and 1 part by mass to 25 parts by mass. By making the aforementioned content of the thermosetting agent (b2) more than the aforementioned lower limit, curing of the film-like adhesive becomes easier. By making the aforementioned content of the thermosetting agent (b2) below the aforementioned upper limit, the moisture absorption rate of the film adhesive is reduced, and the reliability of the package obtained by using the film adhesive is further improved.

In the adhesive composition and the film-like adhesive, the content of the thermosetting component (b) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b2)) relative to the content of the polymer component (a) 100 parts by mass, preferably 5 parts by mass to 100 parts by mass, more preferably 5 parts by mass to 75 parts by mass, particularly preferably 5 parts by mass to 50 parts by mass, for example, 5 parts by mass to 35 parts by mass, And any one of 5 parts by mass to 20 parts by mass. By making the aforementioned content of the thermosetting component (b) within such a range, the peeling force between the intermediate layer and the film-like adhesive becomes more stable.

In order to improve the various physical properties of the film adhesive, the adhesive composition and the film-like adhesive may contain the polymer component (a) and the thermosetting component (b) as necessary. a) and other components of the thermosetting component (b). The other components contained in the adhesive composition and the film-like adhesive are preferably, for example, hardening accelerator (c), filler (d), coupling agent (e), crosslinking agent (f), energy ray Curable resin (g), photopolymerization initiator (h), general additives (i), etc.

[Hardening accelerator (c)] The hardening accelerator (c) is a component used to adjust the hardening speed of the adhesive composition. As a preferable hardening accelerator (c), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be cited; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (one or more Phosphine in which hydrogen atoms are substituted by organic groups); tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

The hardening accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these hardening accelerators (c) may be Free to choose.

In the case of using the curing accelerator (c), in the adhesive composition and the film-like adhesive, the content of the curing accelerator (c) relative to 100 parts by mass of the thermosetting component (b) is 0.01 to 10 parts by mass Parts by mass are better, and more preferably from 0.1 parts by mass to 5 parts by mass. By making the aforementioned content of the hardening accelerator (c) more than the aforementioned lower limit, the effect of using the hardening accelerator (c) becomes more remarkable. By making the content of the hardening accelerator (c) below the aforementioned upper limit, for example, the hardening accelerator (c) of high polarity is prevented from being bonded to the film-like adhesive in the film-like adhesive under the conditions of high temperature and high humidity. The adhesion interface side of the body moves and the effect of segregation becomes higher, and the reliability of the package obtained by using the film-like adhesive is improved.

[Filling material (d)] When the film adhesive contains the filler (d), the cutting property of the film adhesive obtained by spreading is further improved. In addition, by containing the filler (d), the film-like adhesive makes it easy to adjust the thermal expansion coefficient. The thermal expansion coefficient can be optimized with respect to the object to be attached to the film-like adhesive, and the film-like adhesive can be used. The reliability of the package is improved. In addition, by making the film adhesive contain the filler (d), it is also possible to reduce the moisture absorption rate of the film adhesive after curing, or to improve the heat dissipation.

The filler (d) may be any one of an organic filler and an inorganic filler, and an inorganic filler is preferred. Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc.; beads made by spheronizing these inorganic fillers Granules; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among them, the inorganic filler is preferably silica or alumina.

The filler (d) contained in the adhesive composition and the film adhesive may be one type or two or more types. In the case of two or more types, the combination and ratio of these fillers (d) can be arbitrarily selected .

When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all ingredients other than the solvent in the adhesive composition (that is, the ratio of the filler (d) in the film adhesive The ratio of the content relative to the total mass of the film-like adhesive) is preferably 5 mass% to 80 mass%, more preferably 10 mass% to 70 mass%, and particularly preferably 20 mass% to 60 mass%. By making the aforementioned ratio within such a range, the effect brought about by using the aforementioned filler (d) can be obtained more significantly.

[Coupling agent (e)] By containing the coupling agent (e), the film-like adhesive can improve the adhesiveness and adhesion to the adherend. In addition, by containing the coupling agent (e) in the film adhesive, the cured product of the film adhesive can improve water resistance without impairing heat resistance. The coupling agent (e) has a functional group that can react with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound that has a functional group that can react with the functional group of the polymer component (a), the thermosetting component (b), etc., and the silane coupling agent is more preferable.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these coupling agents (e) can be arbitrarily selected .

When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is relative to 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b), It is preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. By making the aforementioned content of the coupling agent (e) above the aforementioned lower limit value, the filler (d) can be used to improve the dispersibility of the filler (d) to the resin or the adhesion of the film-like adhesive to the adherend. (e) The effect brought by it is more significant. By making the aforementioned content of the coupling agent (e) below the aforementioned upper limit value, the generation of outgass can be more suppressed.

[Crosslinking agent (f)] When the polymer component (a) uses the above-mentioned acrylic resin with functional groups such as vinyl, (meth)acrylic, amine, hydroxyl, carboxyl, isocyanate, etc. that can be bonded to other compounds, the adhesive composition The material and the film-like adhesive may also contain a crosslinking agent (f). The cross-linking agent (f) is a component used to make the aforementioned functional groups in the polymer component (a) bond with other compounds to cross-link. By cross-linking in this way, the film-like adhesive can be adjusted Beginning with strength and cohesion.

As the crosslinking agent (f), for example, organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

When an organic polyisocyanate compound is used as the crosslinking agent (f), the polymer component (a) is preferably a hydroxyl-containing polymer. When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the film adhesive can be easily introduced by the reaction between the crosslinking agent (f) and the polymer component (a) Cross-linked structure.

The cross-linking agent (f) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these cross-linking agents (f) may be Free to choose.

When the crosslinking agent (f) is used, in the adhesive composition, the content of the crosslinking agent (f) relative to the content of the polymer component (a) is 100 parts by mass, preferably 0.01 to 20 parts by mass, It is more preferably from 0.1 parts by mass to 10 parts by mass, and particularly preferably from 0.3 parts by mass to 5 parts by mass. By making the aforementioned content of the cross-linking agent (f) above the aforementioned lower limit value, the effect of using the cross-linking agent (f) can be obtained more significantly. By making the aforementioned content of the cross-linking agent (f) below the aforementioned upper limit value, excessive use of the cross-linking agent (f) can be suppressed.

[Energy ray curable resin (g)] By containing the energy-ray curable resin (g) in the adhesive composition and the film-like adhesive, the film-like adhesive can change its characteristics by irradiation with energy rays.

The energy ray curable resin (g) is obtained from an energy ray curable compound. Examples of the aforementioned energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth)acryloyl group are preferred.

The energy ray curable resin (g) contained in the adhesive composition may be only one type or two or more types. In the case of two or more types, the combination and ratio of these energy ray curable resins (g) can be arbitrary choose.

In the case of using energy ray curable resin (g), the ratio of the content of energy ray curable resin (g) in the adhesive composition to the total mass of the adhesive composition is preferably 1% to 95% by mass, It is more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass to 85% by mass.

[Photopolymerization initiator (h)] When the adhesive composition and the film-like adhesive contain energy ray curable resin (g), in order to efficiently polymerize the energy ray curable resin (g), a photopolymerization initiator (h) may also be included .

The photopolymerization initiator (h) in the adhesive composition includes, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin Benzoin compounds such as dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenyl ethyl Acetophenone compounds such as alkane-1-one; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide Isotonic phosphine oxide compounds; benzyl phenyl sulfide, tetramethylthiuram monosulfide and other sulfide compounds; 1-hydroxycyclohexyl phenyl ketone and other α-keto alcohol compounds; azobisisobutyronitrile and other sulfide compounds Nitrogen compounds; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; 4-Diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone And other anthraquinone compounds. In addition, examples of the photopolymerization initiator (h) include photosensitizers such as amines.

The photopolymerization initiator (h) contained in the adhesive composition may be only one type or two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators (h) can be arbitrary choose.

In the case of using the photopolymerization initiator (h), in the adhesive composition, the content of the photopolymerization initiator (h) is 0.1 to 20 parts by mass relative to 100 parts by mass of the energy ray curable resin (g). Parts by mass are better, more preferably from 1 part by mass to 10 parts by mass, and particularly preferably from 2 parts by mass to 5 parts by mass.

[General additives (i)] The general additives (i) can be well-known ones, and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred ones include, for example, plasticizers, antistatic agents, antioxidants, colorants (dyes, pigments), and absorbents. Gas agent and so on.

The general additives (i) contained in the adhesive composition and the film adhesive may be one type or two or more types. In the case of two or more types, the combination and ratio of these general additives (i) can be arbitrarily selected . The content of the adhesive composition and the film-like adhesive is not particularly limited, as long as it is appropriately selected according to the purpose.

[Solvent] The adhesive composition preferably further contains a solvent. The workability of the solvent-containing adhesive composition becomes better. The aforementioned solvent is not particularly limited, but preferable examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1-butanol Alcohols such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds) and the like. The solvent contained in the adhesive composition may be only one type or two or more types. In the case of two or more types, the combination and ratio of these solvents can be arbitrarily selected.

Based on the consideration that the components contained in the adhesive composition can be more uniformly mixed, the solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like.

The content of the solvent in the adhesive composition is not particularly limited, as long as it is appropriately selected in accordance with the types of components other than the solvent, for example.

[Method of manufacturing adhesive composition] The adhesive composition can be obtained by blending the components constituting the adhesive composition. The adhesive composition can be produced by the same method as the adhesive composition described above, except that the types of the compounding components are different, for example.

◇Method of manufacturing semiconductor device manufacturing sheet The aforementioned sheet for manufacturing a semiconductor device can be manufactured by stacking the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is the same as the content described above.

For example, the aforementioned semiconductor device manufacturing sheet can prepare a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive in advance, and these layers can be formed in the order of the substrate, the adhesive layer, the intermediate layer, and the film-like adhesive. It is manufactured by laminating and layering. However, this is an example of a method of manufacturing a sheet for semiconductor device manufacturing.

The aforementioned semiconductor device manufacturing sheet can also be manufactured by, for example, the following method: pre-fabricating two or more intermediate laminates composed of a plurality of layers that constitute the semiconductor device manufacturing sheet, and then bonding these intermediate laminates to each other . The composition of the intermediate laminate can be appropriately selected arbitrarily. For example, a first intermediate laminate (corresponding to the aforementioned support sheet) composed of a base material and an adhesive layer and a second intermediate laminate composed of a laminate of an intermediate layer and a film-like adhesive are prepared in advance , The adhesive layer in the first intermediate laminate and the intermediate layer in the second intermediate laminate are bonded together to manufacture a sheet for manufacturing semiconductor devices. However, this is an example of a method of manufacturing a sheet for semiconductor device manufacturing.

As the aforementioned semiconductor device manufacturing sheet, for example, the area of the first surface of the intermediate layer and the area of the first surface of the film adhesive as shown in FIG. 1 are both smaller than the first surface of the adhesive layer and the first surface of the substrate. In the case of a sheet for manufacturing a semiconductor device having a surface area, a step of processing the intermediate layer and the film-like adhesive to a target size may be additionally performed at any stage of the above-mentioned manufacturing method. For example, in the manufacturing method using the aforementioned second intermediate laminate, a step of processing the intermediate layer and the film-like adhesive in the second intermediate laminate to a target size may be additionally performed to manufacture a semiconductor device manufacturing sheet.

In the case of manufacturing a semiconductor device manufacturing sheet with a release film on the film adhesive, for example, a film adhesive can be prepared on the release film and maintained in this state, and then the remaining layers can be laminated to produce a semiconductor device For the production sheet, after laminating all of the substrate, adhesive layer, intermediate layer, and film-like adhesive, a release film can be laminated on the film-like adhesive to produce a semiconductor device manufacturing sheet. The release film can be maintained until the semiconductor device manufacturing sheet is used, and it can be removed at a necessary stage.

A sheet for manufacturing semiconductor devices having other layers that are not equivalent to any of the substrate, adhesive layer, intermediate layer, film-like adhesive, and release film can be formed by adding the above-mentioned manufacturing method at an appropriate timing, Laminate the steps of this other layer to manufacture.

As an example of a preferable sheet for manufacturing a semiconductor device of the present embodiment, a sheet for manufacturing a semiconductor device can be cited, which includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive; The adhesive layer, the intermediate layer, and the film adhesive are laminated; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; the intermediate layer contains at least a polar resin as the non-silicon resin ; In the aforementioned intermediate layer, the ratio of the content of the aforementioned non-silicone resin to the total mass of the intermediate layer is any of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more One; in the aforementioned intermediate layer, the ratio of the content of the aforementioned non-silicone resin as the polar resin to the total content of the aforementioned non-silicone resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass % Or more and 99% by mass or more; in the aforementioned polar resin, the ratio of the mass of the constituent units with polar groups to the total mass of all constituent units is 5 mass% to 70 mass %, and 7.5% mass% to 55 Mass %, and any one of 10% to 40% by mass.

As another example of the preferred semiconductor device manufacturing sheet of this embodiment, a semiconductor device manufacturing sheet can be cited, which includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive; The adhesive layer, the intermediate layer, and the film-like adhesive are sequentially laminated; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; the intermediate layer contains at least a polar resin as the non-silicon resin Resin; In the intermediate layer, the ratio of the non-silicon resin content to the total mass of the intermediate layer is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more Any one; in the intermediate layer, the ratio of the content of the non-silicon resin as the polar resin to the total content of the non-silicon resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97 Any one of mass% or more and 99% by mass or more; in the aforementioned polar resin, the ratio of the mass of the constituent units with polar groups to the total mass of all constituent units is 5 mass% to 70 mass%, and 7.5 mass% to 55% by mass, and any one of 10% to 40% by mass; when the surface of the film-like adhesive side in the intermediate layer is analyzed by X-ray photoelectron spectroscopy, the concentration of silicon is relative to The ratio of the total concentration of carbon, oxygen, nitrogen, and silicon becomes any one of 1% to 20%, 4% to 16%, and 8% to 12%.

As yet another example of the preferred semiconductor device manufacturing sheet of this embodiment, a semiconductor device manufacturing sheet can be cited, which includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive; The above-mentioned adhesive layer, the above-mentioned intermediate layer, and the above-mentioned film-like adhesive are sequentially laminated on the upper layer; the aforementioned intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; further, it contains a silicon resin; the aforementioned intermediate The layer contains at least a polar resin as the non-silicon resin; in the intermediate layer, the ratio of the content of the non-silicon resin to the total mass of the intermediate layer is 90% to 99.99% by mass, 90% to 97.5% by mass, Any one of 90% to 95% by mass and 90% to 92.5% by mass; in the intermediate layer, the ratio of the content of the silicone resin to the total mass of the intermediate layer is 0.01% to 10% by mass , 2.5% to 10% by mass, 5% to 10% by mass, and 7.5% to 10% by mass; however, in the intermediate layer, the total content of the non-silicon resin and the silicone resin is relatively The proportion of the total mass of the aforementioned intermediate layer does not exceed 100% by mass; in the aforementioned intermediate layer, the proportion of the aforementioned non-silicone resin as the polar resin relative to the total content of the aforementioned non-silicone resin is 80% by mass or more, Any one of 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; among the aforementioned polar resins, the ratio of the mass of the constituent units with polar groups to the total mass of all constituent units is 5 Any one of mass% to 70 mass%, 7.5% to 55% by mass, and 10% to 40% by mass.

As yet another example of the preferred semiconductor device manufacturing sheet of this embodiment, a semiconductor device manufacturing sheet can be cited, which includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive; The above-mentioned adhesive layer, the above-mentioned intermediate layer, and the above-mentioned film-like adhesive are sequentially laminated on the upper layer; the aforementioned intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; further, it contains a silicon resin; the aforementioned intermediate The layer contains at least a polar resin as the non-silicon resin; in the intermediate layer, the ratio of the content of the non-silicon resin to the total mass of the intermediate layer is 90% to 99.99% by mass, 90% to 97.5% by mass, Any one of 90% to 95% by mass and 90% to 92.5% by mass; in the intermediate layer, the ratio of the content of the silicone resin to the total mass of the intermediate layer is 0.01% to 10% by mass , 2.5% to 10% by mass, 5% to 10% by mass, and 7.5% to 10% by mass; however, in the intermediate layer, the total content of the non-silicon resin and the silicone resin is relatively The proportion of the total mass of the aforementioned intermediate layer does not exceed 100% by mass; in the aforementioned intermediate layer, the proportion of the aforementioned non-silicone resin as the polar resin relative to the total content of the aforementioned non-silicone resin is 80% by mass or more, Any one of 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; among the aforementioned polar resins, the ratio of the mass of the constituent units with polar groups to the total mass of all constituent units is 5 Any one of mass% to 70 mass %, 7.5 mass% to 55 mass %, and 10 mass% to 40 mass %; the thickness of the aforementioned intermediate layer is 5 μm to 150 μm, 5 μm to 120 μm, 30 μm to 120 μm, and 60 μm to 120 μm Any of them.

◇Using method of semiconductor device manufacturing sheet (method of manufacturing semiconductor wafer with film adhesive) The aforementioned semiconductor device manufacturing sheet can be used in the manufacture of a semiconductor wafer with a film-like adhesive during the manufacturing process of the semiconductor device. Hereinafter, while referring to the drawings, the method of using the aforementioned semiconductor device manufacturing sheet (the manufacturing method of a semiconductor wafer with a film-like adhesive) will be described in detail.

3A, 3B, and 3C are cross-sectional views schematically illustrating an example of the method of using the semiconductor device manufacturing sheet, and show the case where the semiconductor device manufacturing sheet is attached to a semiconductor wafer and used. In this method, the semiconductor device manufacturing sheet is used as a dicing die. Here, the sheet 101 for manufacturing a semiconductor device shown in FIG. 1 is taken as an example, and the method of use thereof will be described.

First, as shown in FIG. 3A, the semiconductor device manufacturing sheet 101 with the release film 15 removed is heated and the film-like adhesive 14 is attached to the inner surface 9b' of the semiconductor wafer 9'. Symbol 9a' denotes the circuit formation surface of the semiconductor wafer 9.

The heating temperature at the time of attaching the sheet 101 for manufacturing a semiconductor device is not particularly limited, and from the viewpoint of further improving the stability of the heating attaching of the sheet 101 for manufacturing a semiconductor device, 40°C to 70°C is preferable.

_{The maximum value of the width W 13} of the intermediate layer 13 and the maximum value of the width W ₁₄ of the film adhesive 14 in the semiconductor device manufacturing wafer 101 are exactly the same as the maximum value of the width W _{9 ′ of the semiconductor wafer 9 ′, or} Although they are not the same, the error is slight and almost the same.

For example, when the maximum value of the semiconductor wafer 9 _'9 width _W' of 150mm is the case, the intermediate layer 13 of width W and the maximum value of a film ₁₃ followed by the maximum value of the width W ₁₄ of the agent 14 to 150mm to 160mm preferably , when the maximum value of the semiconductor wafer 9 _'9 width _W' of 200mm is the case, the intermediate layer 13 of width W and the maximum value of a film ₁₃ followed by the maximum value of the width W ₁₄ of the agent 14 to 200mm to 210mm preferably, _{When the maximum value of the width W 9 ′} of the semiconductor wafer 9 ′ is 300 mm, the maximum value of the width W ₁₃ of the intermediate layer 13 and the maximum value of the width W ₁₄ of the film adhesive 14 are preferably 300 mm to 310 mm. The difference between the maximum so as, in the present embodiment, the intermediate layer 13 of a width W of the maximum ₁₃ and the semiconductor wafer 9 _'9 of a width _W', the width of the agent and a film 14 followed by the maximum value ₁₄ of the semiconductor W the difference between the maximum wafer 9 'of the width W is _9' of the Jieke 0mm to 10mm. Here, the width W _{9 ′ of the} semiconductor wafer 9 ′ means, for example, the width of the semiconductor wafer 9 ′ in a parallel direction with respect to the inner surface 9 b.

Next, the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9'obtained above is cut with a blade from the circuit forming surface 9a' side of the semiconductor wafer 9'to perform blade dicing, thereby cutting the semiconductor wafer 9 The film adhesive 14 is divided and cut.

Blade cutting can be performed by a known method. For example, in the first surface 12a of the adhesive layer 12 in the semiconductor device manufacturing sheet 101, the region near the periphery of the non-laminated intermediate layer 13 and the film-like adhesive 14 (the aforementioned non-laminated region) can be fixed to a ring frame, etc. After the jig (not shown), the semiconductor wafer 9'is divided and the film adhesive 14 is cut using a blade.

Through this step, as shown in FIG. 3B, a plurality of semiconductor wafers with a film-like adhesive are obtained, which are provided with a semiconductor wafer 9 and a film-like adhesive 140 provided on the inner surface 9b of the semiconductor wafer 9 914. The semiconductor wafers 914 with the film-like adhesive are arranged neatly on the intermediate layer 13 of the laminated sheet 10 and are fixed to form a group of semiconductor wafers 910 with the film-like adhesive. The inner surface 9b of the semiconductor wafer 9 corresponds to the inner surface 9b' of the semiconductor wafer 9'. In addition, in FIG. 3B, reference numeral 9a denotes the circuit formation surface of the semiconductor wafer 9 and corresponds to the circuit formation surface 9a' of the semiconductor wafer 9'.

When dicing with a blade, it is preferable to use a blade to cut the semiconductor wafer 9 into the entire thickness direction of the semiconductor wafer 9'for division, and to cut the semiconductor device manufacturing sheet 101 from the first surface 14a of the film-like adhesive 14 The film-like adhesive 14 is cut in the entire area in the thickness direction of the film-like adhesive 14 up to the middle area of the intermediate layer 13 without cutting into the adhesive layer 12. That is, when the blade is diced, it is preferable to use the blade to cut the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9'along the stacking direction from the circuit forming surface 9a' of the semiconductor wafer 9'to at least The first surface 13a of the intermediate layer 13 is not cut to the surface of the intermediate layer 13 opposite to the first surface 13a (that is, the contact surface with the adhesive layer 12).

In this step, in this way, the blade can be easily prevented from reaching the base material 11, and thereby, the generation of cutting chips from the base material 11 can be suppressed. In addition, the fact that the main component of the intermediate layer 13 cut by the blade is a non-silicon-based resin with a weight average molecular weight of 100,000 or less, especially a weight average molecular weight of 100,000 or less, can also suppress the generation of cutting chips from the intermediate layer 13.

The conditions for blade cutting are not particularly limited as long as they are appropriately adjusted according to the purpose. Generally, the rotation speed of the blade is preferably 15000rpm to 50000rpm, and the moving speed of the blade is preferably 5mm/sec to 75mm/sec.

After the blade is cut, as shown in FIG. 3C, the semiconductor wafer 914 with the film-like adhesive is pulled away from the intermediate layer 13 of the laminated sheet 10 for picking up. Here is shown a situation where the semiconductor wafer 914 with the film-like adhesive is pulled away in the direction of arrow P using the pull-off mechanism 7 such as a vacuum collet. In addition, the pull-off mechanism 7 is not shown in cross section here The semiconductor chip 914 with the film-like adhesive can be picked up by a known method.

When the ratio of the aforementioned silicon concentration on the first surface 13a of the intermediate layer 13 is 1% to 20%, the semiconductor chip 914 with the film-like adhesive can be picked up more easily. When the intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer as the aforementioned non-silicon resin and a silicone compound as the aforementioned additive, the content of the ethylene-vinyl acetate copolymer in the intermediate layer is relative to the total of the intermediate layer The mass ratio is 90% to 99.99% by mass, and the ratio of the content of the aforementioned silicone compound in the intermediate layer to the total mass of the intermediate layer is 0.01% to 10% by mass, making it easier to pick up the film Adhesive-like semiconductor chip 914.

Among the methods for manufacturing semiconductor wafers with film-like adhesives described so far, as a preferred embodiment, for example, a method for manufacturing semiconductor wafers with film-like adhesives can be cited. The semiconductor wafer includes a semiconductor wafer and a film adhesive provided on the inner surface of the semiconductor wafer; the semiconductor device manufacturing sheet includes the substrate, an adhesive layer, an intermediate layer, and a film adhesive; the manufacturing method includes the following Step: heating the semiconductor device manufacturing sheet while attaching the film adhesive in the semiconductor device manufacturing sheet to the inner surface of the semiconductor wafer; attaching the semiconductor device to which the film adhesive is attached The wafer is cut into the entire area in the thickness direction from the circuit formation surface side to be divided to produce the semiconductor wafer, and the semiconductor device manufacturing sheet is cut in the thickness direction from the film-like adhesive side to the middle of the intermediate layer Cut the film-like adhesive as far as the region without cutting into the adhesive layer, thereby obtaining a film-like adhesive in which a plurality of semiconductor wafers with the film-like adhesive are arranged neatly on the intermediate layer The step of semiconductor wafer group; and the step of picking up the semiconductor wafer with the film-like adhesive from the intermediate layer (sometimes referred to as "manufacturing method 1" in this specification).

4A, 4B, and 4C are cross-sectional views schematically illustrating an example of a method for manufacturing a semiconductor wafer, which is the object of use of the semiconductor device manufacturing sheet. The situation of manufacturing semiconductor wafers is shown. 5A, FIG. 5B, and FIG. 5C are cross-sectional views for schematically illustrating other examples of the method of using the semiconductor device manufacturing sheet, and show the case where the semiconductor device manufacturing sheet is attached to the semiconductor chip and used. In this method, the semiconductor device manufacturing sheet is used as a bonding wafer. Here, the sheet 101 for manufacturing a semiconductor device shown in FIG. 1 is taken as an example, and the method of use thereof will be described.

First, before using the semiconductor device manufacturing sheet 101, as shown in FIG. 4A, a semiconductor wafer 9'is prepared, and a back polishing tape (sometimes referred to as "surface") is attached to the circuit formation surface 9a of the semiconductor wafer 9' Protective tape") 8. 4A, the symbols W is _{9 'of} a semiconductor wafer 9' width.

Next, laser light (not shown) is irradiated to focus on the focal point set inside the semiconductor wafer 9', thereby forming a modified layer inside the semiconductor wafer 9'as shown in FIG. 4B 90'. The aforementioned laser light is preferably irradiated to the semiconductor wafer 9'from the inner surface 9b' side of the semiconductor wafer 9'.

The focal position at this time is the predetermined position for dividing (cutting) the semiconductor wafer 9', which is set in such a way that the semiconductor wafers of the target size, shape, and number are obtained from the semiconductor wafer 9'.

Next, a grinder (not shown) is used to grind the inner surface 9b' of the semiconductor wafer 9'. Thereby, the thickness of the semiconductor wafer 9'is adjusted to a target value, and the semiconductor wafer 9'is divided at the formation portion of the modified layer 90' by using the force applied to the semiconductor wafer 9 during grinding at this time , And a plurality of semiconductor wafers 9 are fabricated as shown in FIG. 4C.

The modified layer 90' of the semiconductor wafer 9'is different from other parts of the semiconductor wafer 9', and is degraded and weakened by the irradiation of laser light. Therefore, by applying force to the semiconductor wafer 9'on which the modified layer 90' is formed, the modified layer 90' will be applied with force, and the semiconductor wafer 9'will be broken at the portion of the modified layer 90' to obtain a plurality of A semiconductor wafer 9.

In the above manner, the semiconductor wafer 9 which is the object of use of the semiconductor device manufacturing sheet 101 is obtained. More specifically, through this step, a semiconductor wafer group 901 in which a plurality of semiconductor wafers 9 are arranged neatly and fixed on the back polishing tape 8 is obtained.

When the semiconductor chip group 901 is viewed from above and viewed in a plan view, the planar shape formed by connecting the outermost parts of the semiconductor chip group 901 (such a planar shape is sometimes referred to as "the planar shape of the semiconductor chip group" in this specification). It is exactly the same as the planar shape when looking down on the semiconductor wafer 9', or the difference between these planar shapes is negligible. The aforementioned planar shape of the semiconductor wafer group 901 can be said to be the same as that of the semiconductor wafer 9'. The aforementioned planar shapes are approximately the same. Therefore, the width of the aforementioned planar shape of the semiconductor wafer group 901 can be regarded as the _{same as the width W 9} ′ of the semiconductor wafer 9 ′ as shown in FIG. 4C. In addition, the maximum value of the width of the aforementioned planar shape of the semiconductor chip group 901 can be regarded as the same as the maximum value _{of the width W 9 ′ of the semiconductor wafer 9 ′.}

In addition, although it is shown here that the semiconductor wafer 9 is produced from the semiconductor wafer 9'according to the purpose, according to the conditions of the grinding of the inner surface 9b' of the semiconductor wafer 9', the semiconductor wafer 9'may Part of the area is not divided into semiconductor wafer 9.

Next, the semiconductor wafer 9 (semiconductor wafer group 901) obtained above is used to manufacture a semiconductor wafer with a film-like adhesive. First, as shown in FIG. 5A, while heating one sheet 101 for manufacturing a semiconductor device with the release film 15 removed, the film-like adhesive 14 in the sheet 101 for manufacturing a semiconductor device is attached to The inner surface 9b of all the semiconductor wafers 9 in the semiconductor wafer group 901. At this time, the attachment target of the film-like adhesive 14 may also be a semiconductor wafer that is not completely divided.

_{The maximum value of the width W 13} of the intermediate layer 13 and the maximum value of the width W ₁₄ of the film adhesive 14 in the semiconductor device manufacturing wafer 101 are the same as the width W _{9'of the semiconductor wafer 9'} (in other words, the semiconductor chip group 901 The maximum value of the width) is exactly the same, or, although it is not the same, the error is slight and becomes approximately the same.

That is, the relationship between the intermediate layer 13 of a width W of ₁₃ and a maximum value of the maximum width of the semiconductor wafer and the group 901 may be the above-described width W 13 of the intermediate layer ₁₃ of the maximum width of the semiconductor wafer 9 'of the ₉ the same relationship to a maximum value W _'of. In addition, a film and then the relationship between the maximum value and the maximum width of the semiconductor wafer group 901 of width W ₁₄ of the agent 14 may be described above and then a film of a width W of the agent 14 and the semiconductor wafer ₁₄ of maximum 9 the same relationship to the maximum value 'of the width W _9' of.

At this time, the film adhesive 14 (semiconductor device manufacturing sheet 101) is attached to the semiconductor chip group 901. In addition to replacing the semiconductor wafer 9 with the semiconductor chip group 901, it can be combined with the film in the aforementioned manufacturing method 1. The application of the adhesive 14 (sheet 101 for manufacturing a semiconductor device) to the semiconductor wafer 9'is performed in the same manner.

Next, the back polishing tape 8 is removed from the semiconductor wafer group 901 in the fixed state. In addition, as shown in FIG. 5B, while cooling the semiconductor device manufacturing sheet 101, the surface of the semiconductor device manufacturing sheet 101 (for example, the first surface 12a of the adhesive layer 12) is stretched in the parallel direction, thereby Expand. Here, the semiconductor device manufactured by arrows E ₁ represented by the extended direction of the sheet 101. By expanding in this way, the film-like adhesive 14 is cut along the outer periphery of the semiconductor wafer 9.

Through this step, a plurality of semiconductor wafers 914 with film adhesives, which are provided with the semiconductor wafer 9 and the cut film adhesive 140 provided on the inner surface 9 b of the semiconductor wafer 9, can be obtained. The semiconductor wafers 914 with the film-like adhesive are arranged neatly on the intermediate layer 13 of the laminated sheet 10 and are fixed to form a group of semiconductor wafers 910 with the film-like adhesive. The semiconductor chip 914 with film adhesive and the semiconductor chip group 910 with film adhesive obtained here are the same as the semiconductor wafer 914 with film adhesive and the film adhesive obtained by manufacturing method 1 described above. The semiconductor chip group 910 of the agent is substantially the same.

As mentioned above, when the semiconductor wafer 9'is divided, when a part of the semiconductor wafer 9'is not divided into semiconductor chips 9, this area will be divided into semiconductor chips by performing this step.

The sheet 101 for manufacturing a semiconductor device is preferably expanded at a temperature of -5°C to 5°C. By cooling and expanding the sheet 101 for manufacturing a semiconductor device in this manner (cold expansion), the film-like adhesive 14 can be cut more easily and with high precision.

The expansion of the semiconductor device manufacturing sheet 101 can be performed by a known method. For example, in the first surface 12a of the adhesive layer 12 in the semiconductor device manufacturing sheet 101, the region near the periphery of the non-laminated intermediate layer 13 and the film-like adhesive 14 (the aforementioned non-laminated region) can be fixed to a ring frame, etc. After the jig (not shown in the figure), the entire region of the semiconductor device manufacturing sheet 101 where the intermediate layer 13 and the film-like adhesive 14 are laminated is raised from the substrate 11 in the direction from the substrate 11 to the adhesive layer 12, and This expands the sheet 101 for manufacturing semiconductor devices.

In FIG. 5B, among the first surface 12a of the adhesive layer 12, the non-laminated regions of the unlaminated intermediate layer 13 and the film-like adhesive 14 are substantially parallel to the first surface 13a of the intermediate layer 13, but as described above, When the semiconductor device manufacturing sheet 101 is in an expanded state by the top, the aforementioned non-laminated area will include an inclined surface (as it approaches the outer periphery of the adhesive layer 12, the height decreases in a direction opposite to the above-mentioned top direction).

In this step, since the semiconductor device manufacturing sheet 101 is provided with the intermediate layer 13 (in other words, the film-like adhesive 14 before cutting is provided on the intermediate layer 13), the film-like adhesive 14 can be placed on the target site (in other words, along the semiconductor The outer periphery of the wafer 9) is cut with high precision, and cutting failures can be suppressed.

After the expansion, as shown in FIG. 5C, the semiconductor wafer 914 with the film-like adhesive is pulled away from the intermediate layer 13 of the laminated sheet 10 for picking up. The pick-up at this time can be performed by the same method as the pick-up in the manufacturing method 1 described above, and the pick-up suitability is also the same as the pick-up suitability in the manufacturing method 1.

For example, even in this step, when the ratio of the aforementioned silicon concentration on the first surface 13a of the intermediate layer 13 is 1% to 20%, the semiconductor wafer 914 with the film-like adhesive can be picked up more easily. In addition, when the intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer as the aforementioned non-silicon resin and a silicone compound as the aforementioned additive, the content of the ethylene-vinyl acetate copolymer in the intermediate layer is relative to that of the intermediate layer The ratio of the total mass of the intermediate layer is 90% to 99.99% by mass, and the ratio of the content of the aforementioned silicone compound in the intermediate layer to the total mass of the intermediate layer is 0.01% to 10% by mass, which makes it easier to pick up A semiconductor chip 914 with a film adhesive.

Among the methods for manufacturing semiconductor wafers with film-like adhesives described so far, as a preferred embodiment, for example, a method for manufacturing semiconductor wafers with film-like adhesives can be cited. The semiconductor wafer includes a semiconductor wafer and a film adhesive provided on the inner surface of the semiconductor wafer; the semiconductor device manufacturing sheet includes the substrate, an adhesive layer, an intermediate layer, and a film adhesive; the manufacturing method includes the following Step: the step of irradiating the laser light to the focal point set inside the semiconductor wafer to form a modified layer inside the semiconductor wafer; the semiconductor crystal after the modified layer is formed The inner surface of the circle is ground, and the grinding force applied to the semiconductor wafer is used to divide the semiconductor wafer at the formation position of the modified layer to obtain a plurality of semiconductor wafers in a neatly arranged state. The step of the wafer group; heating the aforementioned semiconductor device manufacturing sheet, while attaching the film-like adhesive in the semiconductor device manufacturing sheet to the inner surfaces of all the semiconductor wafers in the semiconductor wafer group; while attaching The semiconductor device manufacturing sheet attached to the semiconductor wafer is cooled and stretched in a direction parallel to the surface of the film adhesive, thereby cutting the film adhesive along the outer periphery of the semiconductor wafer Step of obtaining a group of semiconductor wafers with a film adhesive in a state where the semiconductor wafers with a film adhesive are neatly arranged on the intermediate layer; and, separating the film adhesive from the intermediate layer The semiconductor chip is used for picking up (sometimes referred to as "manufacturing method 2" in this specification).

So far, any of the manufacturing method 1 and the manufacturing method 2 has cited the semiconductor device manufacturing sheet 101 shown in FIG. The device manufacturing sheet can also be used in the same way. In this case, if necessary, other steps may be appropriately added based on the difference between the configuration of the semiconductor device manufacturing sheet and the semiconductor device manufacturing sheet 101, and the semiconductor device manufacturing sheet may be used.

It is not limited to the case of manufacturing method 1 and manufacturing method 2. After obtaining the semiconductor chip group with the film-like adhesive, before picking up the semiconductor chip with the film-like adhesive, the laminated sheet may be opposed to the adhesive The surface (first surface) on the side of the intermediate layer of the layer expands in the parallel direction, and then maintains this state, and the semiconductor chip with the film-like adhesive is not placed in the laminated sheet (the group of semiconductor wafers with the film-like adhesive) ) To be heated. By adopting this method, while shrinking the peripheral edge portion, the distance between adjacent semiconductor wafers (that is, the slit width) can be maintained sufficiently wide and uniformly on the laminate sheet. In addition, it is easier to pick up semiconductor wafers with a film-like adhesive. (Example)

Hereinafter, the present invention will be explained in more detail through specific examples. However, the present invention is not limited at all to the embodiments shown below.

[Materials for manufacturing adhesive composition] The raw materials used in the manufacture of the adhesive composition are as follows. [Polymer component (a)] (a)-1: Acrylic resin (weight average molecular weight 800,000, glass transition temperature 9°C) copolymerized by methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass). [Epoxy resin (b1)] (b1)-1: Cresol novolac type epoxy resin with acrylic group added ("CNA147" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 518g/eq, number average molecular weight 2100, unsaturated group content and epoxy The base is equivalent). [Thermal Hardener (b2)] (b2)-1: Aralkyl type phenol resin ("Milex XLC-4L" manufactured by Mitsui Chemicals Co., Ltd., number average molecular weight 1100, softening point 63°C). [Filling material (d)] (d)-1: Spherical silicon dioxide ("YA050C-MJE" manufactured by Admatechs, with an average particle size of 50nm, treated with methacrylic acid silane) [Coupling agent (e)] (e)-1: Silane coupling agent, 3-glycidoxypropylmethyl diethoxysilane ("KBE-402" manufactured by Shin-Etsu Polysiloxane) [Crosslinking agent (f)] (f)-1: Toluene diisocyanate-based crosslinking agent ("Coronate L" manufactured by Tosoh)

[Example 1] [Manufacturing of sheets for semiconductor device manufacturing] [Manufacturing of base material] Use an extruder to melt low-density polyethylene (LDPE, "Sumikasen L705" manufactured by Sumitomo Chemical Co., Ltd.), extrude the melt by the T-die method, and stretch the extrudate on a biaxial axis using a cooling roll to obtain Base material made of LDPE (thickness 110μm).

[Making of Adhesive Layer] Manufacture of a non-energy-ray-curable adhesive composition containing acrylic resin ("Oribain BPS 6367X" manufactured by Toyo-Chem) as an adhesive resin (I-1a) ") (100 parts by mass), and a crosslinking agent ("BXX 5640" manufactured by Toyo-Chem) (1 part by mass).

Next, use a peeling film on one side of a polyethylene terephthalate film that has been peeled off by a silicone treatment, and the adhesive composition obtained above is coated on the peeled surface, and heated and dried at 100°C for 2 minutes , To produce a non-energy-ray curable adhesive layer (thickness 10μm).

[Production of Intermediate Layer] At room temperature, ethylene-vinyl acetate copolymer (EVA, weight average molecular weight 30,000, content of constituent units derived from vinyl acetate 25% by mass) (15g) was dissolved in 85g of tetrahydrofuran at room temperature. The resulting solution is added with a silicone compound (polydimethylsiloxane, BYK-333 manufactured by BYK Chemie Japan, with the formula "-Si(-CH ₃ ) _{2 in one molecule"} The number of structural units indicated by "-O-" is 45 to 230) (1.5 g), which is stirred to produce a composition for forming an intermediate layer.

Using a polyethylene terephthalate film with a peeling film on one side that has been peeled off by a silicone treatment, apply the above-obtained composition for forming an intermediate layer on the peeling surface, and heat and dry at 70°C for 5 minutes , Thereby fabricating an intermediate layer (thickness 20 μm).

[Production of Film Adhesive] Manufacture containing polymer component (a)-1 (100 parts by mass), epoxy resin (b1)-1 (10 parts by mass), thermosetting agent (b2)-1 (1.5 parts by mass), filler (d)- A thermosetting adhesive composition of 1 (75 parts by mass), coupling agent (e)-1 (0.5 parts by mass), and crosslinking agent (f)-1 (0.5 parts by mass).

Next, using a peeling film on one side of a polyethylene terephthalate film that has been peeled off by a silicone treatment, the adhesive composition obtained above is coated on the peeling surface, and heated and dried at 80°C for 2 minutes , To produce a thermosetting film-like adhesive (thickness 7μm).

[Manufacturing of sheets for semiconductor device manufacturing] The exposed surface on the side opposite to the side with the release film in the adhesive layer obtained above was bonded to one surface of the substrate obtained above to produce a first intermediate laminate having a release film (in other words, with Support sheet for peeling film). The exposed surface on the side opposite to the side with the release film in the film-like adhesive obtained above and the exposed surface on the side opposite to the side with the release film in the intermediate layer obtained above were bonded to produce the first with release film 2 Intermediate laminate (a laminate of release film, intermediate layer, film adhesive, and release film).

Next, use a cutting knife to press the second intermediate laminate with the release film from the release film on the intermediate layer side to the film-like adhesive to remove unnecessary parts to produce the second intermediate laminate with the release film Processed product, on the release film on the side of the film adhesive, there is a circular (diameter 305mm) film adhesive (thickness 7μm), an intermediate layer (thickness 20μm) and the release film in the thickness direction in this order Constructed on top of the stack.

Next, the release film is removed from the first intermediate laminate with release film obtained above, so that one side of the adhesive layer is exposed. Furthermore, the round release film was removed from the second intermediate laminate processed product with release film obtained above, so that one side of the intermediate layer was exposed. Next, the newly formed exposed surface of the adhesive layer in the first intermediate laminate and the newly formed exposed surface of the intermediate layer in the second intermediate laminate are bonded together. For the substrate and the adhesive layer (ie, support sheet) in the laminate obtained by this, the planar shape of the substrate and the adhesive layer (support sheet) becomes a circle (diameter 370mm), which is similar to a circular film In a way that the adhesive and the intermediate layer (diameter 305mm) are concentric, use a cutting knife (diameter 370mm) to press from the base material side to remove unnecessary parts. By the above method, the substrate (thickness 110μm), the adhesive layer (thickness 10μm), the intermediate layer (thickness 20μm), the film adhesive (thickness 7μm) and the release film are laminated in this order in the thickness direction. The structure of the semiconductor device manufacturing sheet with a release film.

[Evaluation of Semiconductor Device Manufacturing Sheets] [Calculation of the silicon concentration ratio in the film-like adhesive side surface of the intermediate layer] In the manufacturing process of the above-mentioned semiconductor device manufacturing sheet, the exposed surface of the intermediate layer at the stage before bonding with the adhesive layer was analyzed by XPS to determine carbon (C), oxygen (O), and nitrogen (N) And the concentration of silicon (Si) (atomic %), and calculate the ratio (%) of the silicon concentration to the total concentration of carbon, oxygen, nitrogen and silicon based on the measured value. XPS analysis was performed using an X-ray photoelectron spectroscopic analyzer ("Quantra SXM" manufactured by Ulvac) under the conditions of an irradiation angle of 45°, an X-ray beam diameter of 20μmφ, and an output of 4.5W. Show the result and the ratio (%) of the concentration of other elements in the column of "The ratio of the element concentration of the intermediate layer (%)" in Table 1.

[Evaluation of the effect of suppressing cutting chips during cutting of the blade] [Manufacturing of silicon chip group with film adhesive] In the semiconductor device manufacturing sheet obtained above, the release film was removed. Use a silicon wafer (diameter 300mm, thickness 75μm) that has been polished on the inner surface by dry polishing. On the inner surface (polished surface) of the silicon wafer, use a tape machine (made by Lintec) Adwill RAD2500"), while heating the above-mentioned semiconductor device manufacturing sheet to 60°C, it is attached with the film-like adhesive of the semiconductor device manufacturing sheet. Thereby, a laminate composed of a substrate, an adhesive layer, an intermediate layer, a film-like adhesive, and a silicon wafer layered in the thickness direction of these layers (comprised of the aforementioned laminate sheet, film-like adhesive and silicon wafer) is obtained. These are laminated in the thickness direction in order to form a laminate).

Next, the area near the peripheral edge of the first surface of the adhesive layer in the laminate (the non-laminated area) on the first surface where the intermediate layer is not provided is fixed to the ring frame for wafer dicing. Next, a dicing device ("DFD6361" manufactured by Disco) is used for dicing, thereby dividing the silicon wafer and cutting the film-like adhesive to obtain a silicon wafer with a size of 8mm×8mm. The dicing at this time is to set the rotation speed of the blade to 30000rpm and the moving speed of the blade to 30mm/sec. For the semiconductor device manufacturing sheet, the blade is attached from the silicon wafer of the film adhesive of the semiconductor device manufacturing sheet. The surface is cut to the midway area of the intermediate layer (that is, the entire area in the thickness direction of the film adhesive and the intermediate layer from the surface on the film adhesive side to the midway area). The blade system uses "Z05-SD2000-D1-90CC" made by Disco. By the above method, a group of silicon wafers with a film-like adhesive is obtained, which is composed of silicon wafers and a film-like adhesive after cutting provided on the inner surface of the silicon wafer. The film-like adhesive is neatly arranged and fixed on the intermediate layer of the aforementioned laminated sheet.

[Evaluation of the effect of suppressing the generation of cutting chips] Using a digital microscope (“VH-Z100” manufactured by Keyence Corporation), observe the group of silicon wafers with a film-like adhesive obtained above from the upper side of the silicon wafer to confirm whether cutting chips are generated. In addition, it is judged as "A" when no chips are generated at all, and it is judged as "B" when chips are generated even though it is a little. The results are shown in Table 1.

[Evaluation of the cutting performance of the film-like adhesive during expansion] [Manufacturing of silicon chip group with film adhesive] A silicon wafer with a circular planar shape, a diameter of 300 mm, and a thickness of 775 μm is used, and a back polishing tape (“Adwill E-3100TN” manufactured by Lintec Corporation) is attached to one side of the silicon wafer. Second, a laser light irradiation device ("DFL73161" manufactured by Disco) is used to irradiate the laser light to the focal point set inside the silicon wafer, thereby forming the inside of the silicon wafer Modified layer. At this time, the aforementioned focus is set in such a way that a plurality of silicon wafers with a size of 8mm×8mm are obtained from the silicon wafer. In addition, the laser beam irradiates the silicon wafer from the other side (the side on which the back grinding tape is not attached). Secondly, use a grinder to grind the other side of the silicon wafer to adjust the thickness of the silicon wafer to 30μm, and use the grinding force applied to the silicon wafer at this time to apply the modified layer The formation part of the silicon wafer is divided to produce a plurality of silicon wafers. Thereby, a group of silicon wafers in which a plurality of silicon wafers are neatly arranged and fixed on the back polishing belt is obtained.

Next, using a tape attaching machine ("Adwill RAD2500" manufactured by Lintec Corporation), one of the above-obtained semiconductor device manufacturing sheets was heated to 60°C while the film in the semiconductor device manufacturing sheet was heated. The adhesive is attached to the other surface (in other words, the grinding surface) of all the silicon wafers (silicon wafer group). Next, the area (the aforementioned non-layered area) near the periphery of the adhesive layer on the first surface of the semiconductor device manufacturing sheet attached to the silicon wafer group where the intermediate layer is not provided is fixed to the wafer dicing ring frame.

Secondly, remove the back polishing tape from the silicon wafer group in the fixed state. Secondly, using a fully automatic die separator ("DDS2300" manufactured by Disco), the semiconductor device manufacturing sheet is cooled in an environment of 0°C, while being aligned with the surface of the semiconductor device manufacturing sheet. Expand in a parallel direction, thereby cutting the film-like adhesive along the periphery of the silicon wafer. At this time, by fixing the peripheral edge of the semiconductor device manufacturing sheet, the entire region of the semiconductor device manufacturing sheet where the intermediate layer and the film-like adhesive are laminated is raised to a height of 15 mm from the substrate side to expand. Thereby, a plurality of silicon wafers with a film adhesive, which are provided with a silicon wafer and a film adhesive provided on the other surface (grinding surface), are arranged in a neatly arranged state and fixed on the intermediate layer. Silicon chip group with film adhesive.

Next, after temporarily canceling the expansion of the aforementioned semiconductor device manufacturing sheet, at room temperature, the substrate, adhesive layer, and intermediate layer are laminated to form a laminate (that is, the aforementioned laminate sheet) relative to the adhesive layer. The first surface is expanded in a parallel direction. Furthermore, while maintaining the expanded state, the peripheral portion of the silicon wafer with the film-like adhesive not placed on the laminated sheet is heated. As a result, the peripheral edge portion is contracted, and the width of the cut between adjacent silicon wafers on the laminate sheet is maintained at a certain value or more.

[Evaluation of cutting performance of film adhesive] In the manufacture of the above-mentioned silicon wafer group with a film-like adhesive, a digital microscope (“VH-Z100” manufactured by Keyence Corporation) was used to compare the above-mentioned silicon wafer group with a film-like adhesive from silicon Observe the upper side of the wafer side. In addition, confirm the number of the following cutting lines, and evaluate the cutting properties of the film adhesive according to the following evaluation criteria. The above cutting lines assume that the film adhesive is normal by the expansion of the semiconductor device manufacturing sheet In the case of cutting, the cutting lines of a plurality of film-like adhesives extending in one direction and the cutting lines of a plurality of film-like adhesives extending in a direction orthogonal to the direction must be formed. Incomplete cut lines and incomplete cut lines. The results are shown in Table 1. (Evaluation criteria) A: The total number of the cutting lines of the film-like adhesive that is not actually formed and the cutting lines of the film-like adhesive that is not completely formed is 5 or less. B: The total number of cutting lines of the film-like adhesive that is not actually formed and the cutting lines of the film-like adhesive that is not completely formed is 6 or more.

[Evaluation of the pick-up of expanded silicon wafer with film adhesive] After the evaluation of the cutting performance of the above-mentioned film-like adhesive, a silicon chip group with a film-like adhesive and a die-bonding device ("PU100" manufactured by Fasford Technology) were used. The top height was 250μm and the top The conditions of speed 5mm/s and top-up time 500ms pick up silicon wafers with film-like adhesive from the intermediate layer in the aforementioned laminate. In addition, it is evaluated as "A" when all silicon wafers with film-like adhesive can be picked up normally, and "B" when it is impossible to pick up more than one silicon wafer with film-like adhesive normally. The results are shown in Table 1.

[Measurement of T peel strength between the intermediate layer and the film adhesive] In the semiconductor device manufacturing sheet obtained above, the release film was removed. The whole surface of the exposed surface of the film-like adhesive in the sheet for manufacturing semiconductor devices thus produced was attached to an adhesive tape having a polyethylene terephthalate layer (manufactured by Lintec) The adhesive surface of PET50(A) PL thin 8LK”) is cut out with a size of 50mm×100mm to make a test piece. In this test piece, according to JIS K6854-3, the laminate of the base material, the adhesive layer and the intermediate layer (that is, the laminate sheet), the laminate of the film-like adhesive and the adhesive tape are torn apart, thereby making the test The sheet was peeled off in a T-shape, and the maximum peel force (mN/50mm) measured at this time was used as the T-shape peel strength. At this time, the peeling speed was set to 50 mm/min, and the measurement was performed at 23° C. and humidity 50% RH. The results are shown in Table 1.

[Manufacturing and Evaluation of Sheets for Semiconductor Device Manufacturing] [Example 2] The coating amount of the composition for forming the intermediate layer was increased, and the thickness of the intermediate layer was replaced with 80 μm for 20 μm. The same method as in Example 1 was used to manufacture and evaluate the semiconductor device manufacturing sheet. The results are shown in Table 1.

[Example 3] When preparing the composition for forming the intermediate layer, the silicone compound is not added, and the amount of the ethylene-vinyl acetate copolymer used is 16.5g instead of 15g (in other words, the silicone compound is the same mass The aforementioned ethylene-vinyl acetate copolymer was replaced, except that only the aforementioned ethylene-vinyl acetate copolymer was dissolved in tetrahydrofuran, the same method as in Example 1 was used to manufacture and evaluate the semiconductor device manufacturing sheet . The results are shown in Table 1. The entry "-" in the additive column in Table 1 means that this additive is not used.

[Comparative Example 1] When making the composition for forming the intermediate layer, replace the aforementioned ethylene-vinyl acetate copolymer with the same mass of ethylene-vinyl acetate copolymer (EVA, weight average molecular weight 200,000, content of constituent units derived from vinyl acetate) 25% by mass), and increase the coating amount of the composition for forming the intermediate layer, and replace the thickness of the intermediate layer with 80μm instead of 20μm, except that the same method as in Example 1 was used to manufacture the semiconductor device manufacturing sheet And evaluate it. The results are shown in Table 1.

[Comparative Example 2] When making the composition for forming the intermediate layer, replace the aforementioned ethylene-vinyl acetate copolymer with the same mass of ethylene-vinyl acetate copolymer (EVA, weight average molecular weight 200,000, content of constituent units derived from vinyl acetate) 25% by mass). Except for this, the semiconductor device manufacturing sheet was manufactured and evaluated in the same method as in the case of Example 1. The results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 The composition of the middle layer main ingredient Ingredient name EVA EVA EVA EVA EVA Weight average molecular weight 30000 30000 30000 200000 200000 Content (mass%) 90.9 90.9 100 90.9 90.9 additive Ingredient name Polydimethylsiloxane Polydimethylsiloxane - Polydimethylsiloxane Polydimethylsiloxane Content (mass%) 9.1 9.1 - 9.1 9.1 Thickness (μm) 20 80 20 80 20 Evaluation results The ratio of element concentration in the middle layer (%) C 66 66 81 70 70 O 25 25 19 twenty two twenty two N 0 0 0 0 0 Si 9 9 0 8 8 The effect of suppressing the generation of chips when the blade is cutting A A A B B The cutting performance of the film-like adhesive during expansion A A A A B Pickup of expanded silicon chip with film adhesive A A B A A T peel strength between the middle layer and the film adhesive (mN/50mm) 100 60 200 60 100

From the above results, it is obvious that in Examples 1 to 3, the generation of cutting chips can be suppressed when the blade is diced, and the cutting failure of the film-like adhesive can be suppressed when the blade is expanded, and the splitting suitability of the semiconductor wafer is excellent. In Examples 1 to 3, the weight average molecular weight of the ethylene-vinyl acetate copolymer as the main component contained in the intermediate layer of the semiconductor device manufacturing sheet was 30,000.

In addition, in Examples 1 to 3, the ratio of the content of the ethylene-vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90.9% by mass or more, and the content of the silicone compound is relative to The ratio of the total mass in the intermediate layer is 9.1% by mass or less.

In addition, in Examples 1 to 2, the expanded silicon wafer with a film-like adhesive has excellent pick-up properties. In Examples 1 to 2, the T-peel strength between the intermediate layer and the film-like adhesive is less than 100mN/50mm, which is moderately low. In addition, the ratio of the aforementioned silicon concentration in the intermediate layer is 9%, which is moderately changed. Taller. These evaluation results match the evaluation results of the pick-up properties of the silicon wafer with the film-like adhesive described above. In Example 3, the intermediate layer in the sheet for manufacturing a semiconductor device does not contain the aforementioned siloxane-based compound.

The difference between the semiconductor device manufacturing sheets of Example 1 to Example 2 is only the thickness of the intermediate layer. The semiconductor device manufacturing sheet of Example 2 is compared with the semiconductor device manufacturing sheet of Example 1 in the intermediate layer and film-like adhesion The T-shaped peeling strength between the agents is relatively small. Compared with Example 1, the silicon wafer with the film-like adhesive is easier to pick up in Example 2 than in Example 1. It is presumed that this is because even if the ratio (mass %) of the content of the silicone compound in the intermediate layer to the total mass of the intermediate layer (mass %) is used, the semiconductor device manufacturing wafers of Examples 1 to 2 are the same. However, the content (parts by mass) of the silicone compound in the intermediate layer in Example 2 is more than that in Example 1. Furthermore, the silicone compound in the intermediate layer tends to be concentrated on both sides of the intermediate layer and In the vicinity, the amount of siloxane compounds concentrated on both sides of the intermediate layer and the vicinity thereof is also greater in Example 2 than in Example 1.

In addition, in Examples 1 to 3, no nitrogen was detected in the XPS analysis of the exposed surface of the intermediate layer.

In contrast, in Comparative Example 1 to Comparative Example 2, the generation of cutting chips during blade dicing could not be suppressed, and the suitability for dividing the semiconductor wafer was poor. In Comparative Examples 1 to 2, the weight average molecular weight of the ethylene-vinyl acetate copolymer contained as the main component in the intermediate layer of the sheet for manufacturing a semiconductor device was 200,000.

In addition, the difference between the semiconductor device manufacturing sheets of Comparative Example 1 to Comparative Example 2 is only the thickness of the intermediate layer. The relationship between the T-shaped peel strength of the intermediate layer and the film adhesive in Comparative Example 1 to Comparative Example 2 shows The same tendency as in the case of Example 1 to Example 2. In addition, Comparative Example 1 to Comparative Example 2 also did not detect nitrogen during the XPS analysis of the exposed surface of the intermediate layer. [Industry Availability]

The present invention can be used to manufacture semiconductor devices.

1: Support sheet 7: Pull-off mechanism 8: Back grinding tape (surface protection tape) 9': Semiconductor wafer 9a': Circuit formation surface of semiconductor wafer 9b': Inner surface of semiconductor wafer 10: Laminated sheet 11: Substrate 11a: the first side of the substrate 12: the adhesive layer 12a: the first side of the adhesive layer 13: the middle layer 13a: the first side of the middle layer 14: the film-like adhesive 14a: the first side of the film-like adhesive 1 side 15: peeling film 90': modified layer 101: sheet for semiconductor device manufacturing 140: film adhesive 901: semiconductor wafer group 910: semiconductor wafer group with film adhesive 914: semiconductor with film adhesive Chip E ₁ : Expansion direction P: Arrow W ₉ ': Width of the semiconductor wafer W ₁₃ : Width of the intermediate layer W ₁₄ : Width of the film adhesive

Fig. 1 is a cross-sectional view schematically showing a sheet for manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 2] is a plan view of the sheet for manufacturing the semiconductor device shown in Fig. 1. [Fig. [FIG. 3A] is a cross-sectional view for schematically explaining an example of a method of using a semiconductor device manufacturing sheet according to an embodiment of the present invention. [FIG. 3B] is a cross-sectional view for schematically explaining an example of a method of using a semiconductor device manufacturing sheet according to an embodiment of the present invention. [FIG. 3C] is a cross-sectional view for schematically explaining an example of the method of using the semiconductor device manufacturing sheet according to an embodiment of the present invention. [FIG. 4A] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer. [FIG. 4B] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer. [FIG. 4C] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer. [FIG. 5A] is a cross-sectional view for schematically explaining another example of the method of using the semiconductor device manufacturing sheet according to one embodiment of the present invention. [FIG. 5B] is a cross-sectional view for schematically explaining another example of the method of using the semiconductor device manufacturing sheet according to one embodiment of the present invention. [FIG. 5C] is a cross-sectional view for schematically explaining another example of the method of using the semiconductor device manufacturing sheet according to one embodiment of the present invention.

1: Support piece

10: Multilayer film

11: Substrate

11a: The first side of the substrate

12: Adhesive layer

12a: The first side of the adhesive layer

13: middle layer

13a: The first side of the middle layer

14: Film adhesive

14a: First side of film adhesive

15: Peel off the film

101: Sheets for semiconductor device manufacturing

W ₁₃ : the width of the middle layer

W ₁₄ : Width of film adhesive

Claims (3)

A sheet for manufacturing a semiconductor device, comprising a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive; It is formed by sequentially laminating the adhesive layer, the intermediate layer and the film adhesive on the substrate; The aforementioned intermediate layer contains a non-silicone resin having a weight average molecular weight of 100,000 or less as a main component. The semiconductor device manufacturing sheet according to claim 1, wherein when the surface of the film-like adhesive side in the intermediate layer is analyzed by X-ray photoelectron spectroscopy, the concentration of silicon is relative to that of carbon and oxygen. The ratio of the total concentration of, nitrogen and silicon is 1% to 20%. The semiconductor device manufacturing sheet according to claim 1 or 2, wherein the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin, and a silicone-based compound; In the aforementioned ethylene-vinyl acetate copolymer, the ratio of the mass of the constituent units derived from vinyl acetate to the total mass of all constituent units is 10% to 40% by mass; In the aforementioned intermediate layer, the ratio of the content of the aforementioned ethylene-vinyl acetate copolymer to the total mass of the aforementioned intermediate layer is 90% to 99.99% by mass; In the intermediate layer, the ratio of the content of the silicone compound to the total mass of the intermediate layer is 0.01% to 10% by mass.

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