WO2013141072A1

WO2013141072A1 - Pressure-sensitive adhesive tape for protecting semiconductor wafer surface

Info

Publication number: WO2013141072A1
Application number: PCT/JP2013/056752
Authority: WO
Inventors: 啓時横井; 具朗内山
Original assignee: 古河電気工業株式会社
Priority date: 2012-03-19
Filing date: 2013-03-12
Publication date: 2013-09-26
Also published as: CN104185896A; JP2013225647A; SG11201405798SA; JP5367903B2; TW201339277A; KR20140138693A; CN104185896B; TWI462987B; MY161110A

Abstract

A pressure-sensitive adhesive tape for protecting a semiconductor wafer surface for which either the adhesive force when peeling under heat at 50°C from an SUS 280 polished surface, or the adhesive force after irradiation with a 500-mJ ultraviolet beam, is no more than 1.0 N/25 mm, and is no more than 50% of the adhesive force prior to heating or irradiation with an ultraviolet beam. The tape has an adhesive layer on a substrate film, the substrate film having a total thickness of 50 to 200 µm. The thickness of the adhesive layer is 10 to 50 µm. The ratio of the high-modulus-layer thickness to the low-modulus-layer thickness is 1:9 to 5:5. The high-modulus layer is disposed on the rear surface of the adhesive layer, and has a thickness of at least 10 µm, the high-modulus layer comprising polypropylene or a straight-chain polyethylene. The low-modulus layer comprises an ethylene-vinyl acetate copolymer having an MFR of 0.8 to 10 g/10 min and a vinyl acetate content of 5-20 percent by mass.

Description

Adhesive tape for semiconductor wafer surface protection

The present invention relates to an adhesive tape for protecting a semiconductor wafer surface. More specifically, the present invention relates to a surface protecting adhesive tape used when grinding a semiconductor wafer into a thin film.

A semiconductor package is manufactured by slicing a high-purity silicon single crystal or the like into a semiconductor wafer, and then forming an integrated circuit on the wafer surface by ion implantation, etching, or the like. By grinding or polishing the back surface of the semiconductor wafer on which the integrated circuit is formed, the semiconductor wafer has a desired thickness. At this time, in order to protect the integrated circuit formed on the surface of the semiconductor wafer, an adhesive tape for protecting the surface of the semiconductor wafer is used. The back-ground semiconductor wafer is stored in a semiconductor wafer cassette after the back-side grinding is completed, transported to a dicing process, and processed into semiconductor chips.

Conventionally, the thickness of a semiconductor wafer has been reduced to about 200 to 400 μm by backside grinding. In particular, memory devices are becoming thinner and larger in diameter, and a 12-inch semiconductor wafer is often ground to 100 μm or less or 50 μm or less. Therefore, various apparatuses have been developed in order to realize conveyance of large-diameter thin film wafers, and a number of dedicated thin-film grinding machines called in-line systems and dedicated manufacturing methods (see Patent Document 1) have been introduced. .

On the other hand, since discrete wafers and power wafers are rarely stacked like memory devices, thinning has not progressed much compared to memory wafers. However, in recent years, demands such as cloud computing and collective power management have increased, and the thinning of power devices and discrete devices has been accelerated in order to control large currents. A discrete device has a structure in which a current flows from the front electrode to the back electrode, and the resistance decreases as the thickness of the semiconductor wafer decreases, so that the device is a high-performance device. As the required performance is improved, the need to grind to 100 μm or less has increased, and the demand for thin film grinding of discrete wafers has increased.

¡Discrete devices have not been increased in diameter due to the small chip size, and semiconductor wafers of 5 to 6 inches are the mainstream. Since the in-line equipment described above is a dedicated machine that supports 8 inches or more, most of the discrete wafers are ground by old equipment, and the process of etching the back surface after grinding is essential. Therefore, since it is not directly applied to the dicing tape or the dicing die bonding tape immediately after grinding, the in-line device is practically not used and the demand for warpage is higher than that of the memory device.

For these problems, various developed products exist as surface protection tapes for thin film grinding, such as developed products using a polyethylene terephthalate (PET) -based substrate that is a rigid substrate (see Patent Documents 2 and 3). Although many are disclosed, if it carries out to an etching, a base material will melt or discolor and it cannot use as it is. In addition, there are many semiconductor wafers with small steps in memory wafers, but because discrete wafers have large steps or the number of steps is extremely large due to the small chip size, the etching solution is allowed to enter and the device is The problem that destroys occurs.

Furthermore, as an improvement of the surface protection tape for thin film grinding, attempts have been made to cover the infiltration of the etching solution by increasing the thickness of the adhesive. This will cause problems such as the adhesive component melting out. For this reason, it is not easy to thin-film grind discrete wafers. In addition, increasing the thickness of the adhesive layer increases the risk of cohesive failure, which may increase the risk of adhesive residue and cause a problem of adhesive residue, leading to a satisfactory solution. Not in. Moreover, although the improvement of a manufacturing method (refer patent document 4) etc. is disclosed, when ultraviolet irradiation is performed before an etching, the adhesive force will fall, and the problem that a tape peels depending on the kind of semiconductor wafer generate | occur | produced will generate | occur | produce. The solution is not satisfactory. Further, although improvement by an etching method (see Patent Document 5) is also disclosed, in a method using a polyethylene terephthalate (PET) base film in a single layer, the acid resistance against an etching solution containing sulfuric acid is weak, and the base film is On the other hand, the method of using a polypropylene (PP) base film as a single layer causes corrosion of the semiconductor wafer due to deterioration of the grindability of the thinned semiconductor wafer and edge chipping, resulting in peeling failure and adhesive residue. In any case, no satisfactory solution has been reached.

JP 2006-351790 A JP 2011-151355 A JP 2003-261842 A JP-A-5-195255 JP-A-4-251931

The present invention relates to a surface protection tape used in a semiconductor manufacturing process in which an etching process such as a discrete wafer or a power device wafer is used as an adhesive tape for protecting the surface of a semiconductor wafer. An adhesive tape for protecting the surface of a semiconductor wafer that can be made into a thin film wafer of 100 μm or less without invading dust and water even when the back surface of the wafer is ground, and that can be used for an etching process while the surface protective tape is bonded. The issue is to provide.

As a result of intensive studies to solve the above-mentioned problems, the present inventors set the thickness of the pressure-sensitive adhesive layer to a specific thickness, and heated at 50 ° C. in the relationship of the adhesive strength to the SUS280 polished surface of the adhesive tape for semiconductor wafer surface protection. Either the adhesive strength at the time of peeling or the adhesive strength after irradiation with ultraviolet rays of 500 mJ is 1.0 N / 25 mm or less and 50% or less of the adhesive strength when not heated or not irradiated with ultraviolet rays. It has been found that the above problem can be solved by using a specific composite base film (part of the base film is polypropylene or linear polyethylene) as the material film. The present invention has been made based on this finding.

That is, the subject of this invention was solved by the following means.
(1) A semiconductor wafer surface protecting adhesive tape having an adhesive layer on a substrate film,
The base film is a composite base film having a total thickness of 50 μm to 200 μm and comprising a high modulus layer and a low modulus layer, and the ratio of the thickness of the high modulus layer and the low modulus layer The thickness of the high elastic modulus layer: the thickness of the low elastic modulus layer) is in the range of 1: 9 to 5: 5,
The high elastic modulus layer is disposed on the back surface of the pressure-sensitive adhesive layer (the surface opposite to the surface on which the pressure-sensitive adhesive layer of the base film is applied), and has a thickness of 10 μm or more made of polypropylene or linear polyethylene Layer,
The low elastic modulus layer comprises an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 20% by mass and an MFR of 0.8 to 10 g / 10 min.
The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape for protecting a semiconductor wafer surface is 10 μm to 50 μm. A pressure-sensitive adhesive tape for protecting a semiconductor wafer, characterized by being not more than 0.0 N / 25 mm and not more than 50% of the adhesive strength when not heated or not irradiated with ultraviolet rays.
(2) The resin of the high elastic modulus layer is a linear polyethylene having a density of 0.910 to 0.970 g / cm ³ and an MFR of 10 g / 10 min or less. The adhesive tape for semiconductor wafer surface protection of description.
(3) The semiconductor according to (1) or (2), wherein the high elastic modulus layer and the low elastic modulus layer of the base film are laminated without using other materials of an adhesive. Adhesive tape for wafer surface protection.
(4) The pressure-sensitive pressure-sensitive adhesive layer is a pressure-sensitive pressure-sensitive adhesive, and is used in a semiconductor processing process including an etching step. (1) to (3) For protecting a semiconductor wafer surface according to any one of (1) to (3) Adhesive tape.
(5) The adhesive tape for protecting a semiconductor wafer surface according to any one of (1) to (4), wherein the base film is polypropylene or linear polyethylene which is biaxially stretched. .
(6) The adhesive tape for protecting a semiconductor wafer surface according to any one of (1) to (5), wherein the tack force is 60 to 200 kPa.
(7) The adhesive tape for protecting a semiconductor wafer surface according to any one of (1) to (6), wherein the adhesive layer is an emulsion adhesive.
(8) The adhesive tape for protecting a semiconductor wafer surface according to (7), wherein the emulsion-based pressure-sensitive adhesive layer does not contain a water-dispersible isocyanate crosslinking agent.

In the present invention, the above “adhesive strength” means that a 2 kg rubber roller is reciprocated by 3 reciprocations on the adherend, left for 1 hour, and then peeled by 180 degrees using a tensile tester conforming to JIS B 7721. The adhesive strength when measured at 300 mm / min. In addition, the measurement conditions of “when not heated”, “when not irradiated with ultraviolet rays”, and “after irradiation with ultraviolet rays” are all values obtained at 24 ° C. and 50% relative humidity. The SUS polished surface refers to the surface of a SUS steel sheet having a thickness of 1.5 mm to 2.0 mm specified in JIS G 4305 finished with 280th water-resistant abrasive paper specified in JIS R 6253.

Even when the semiconductor wafer surface protective adhesive tape of the present invention is bonded to the surface of a semiconductor wafer (for example, a discrete wafer), the back surface of the semiconductor wafer is ground to form a thin film wafer of 100 μm or less. In addition, the semiconductor wafer can be processed without any problem even in the etching process with the adhesive tape for protecting the surface of the semiconductor wafer being bonded. That is, even in the dipping etching process, polishing of the back surface of the wafer can be performed without allowing the ingress of acid. Further, when the adhesive tape for protecting the surface of the semiconductor wafer is peeled off, it can be easily peeled without any adhesive residue.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

FIG. 1 is an enlarged cross-sectional view illustrating an embodiment of the adhesive tape for protecting a semiconductor wafer surface according to the present invention. FIG. 2 is an explanatory diagram of a method for measuring the adhesive force of the adhesive tape for protecting a semiconductor wafer surface of the present invention.

The preferred adhesive tape for protecting the surface of a semiconductor wafer of the present invention will be described with reference to the drawings.

Hereinafter, embodiments of the present invention will be described in detail.
In the adhesive tape for protecting a semiconductor wafer surface of the present invention, at least one type of adhesive 23 is applied to at least one surface of the base film 20 to form an adhesive layer. FIG. 1 shows an example of a base film 20 composed of a plurality of layers of a back surface 21 and a front surface 22 and an adhesive layer 23 in the cross section of the semiconductor wafer surface protecting adhesive tape.

(Adhesive layer)
The pressure-sensitive adhesive layer 23 of the present invention may be composed of one type of pressure-sensitive adhesive layer, or two or more different types of pressure-sensitive adhesive layers may be laminated. The thickness of the pressure-sensitive adhesive layer is 10 μm to 50 μm. is there. If it is less than 10 μm, it cannot cope with a step such as a scribe line on the surface of the semiconductor wafer, so that dust intrusion or etching liquid intrusion occurs and the surface cannot be sufficiently protected. On the other hand, if it exceeds 50 μm, the cross-sectional area of the pressure-sensitive adhesive layer becomes large, and problems such as dissolution of the pressure-sensitive adhesive into the etching liquid and adhesive residue due to insufficient cohesive force occur. Further, the pressure-sensitive adhesive of the pressure-sensitive adhesive layer may be either pressure-sensitive or ultraviolet curable, but pressure-sensitive pressure-sensitive adhesives are preferred. In the case of the pressure-sensitive adhesive, since it is heated and peeled at the time of peeling, the adhesive strength to the SUS280 polished surface at the time of heat peeling at 50 ° C. is 50% or less compared with the adhesive strength at the time of normal peeling, and 1.0 N / 25 mm or less. On the other hand, when an ultraviolet curing adhesive is used, the adhesive strength to the SUS280 polished surface after UV curing of 500 mJ is similarly 50% or less with respect to the adhesive strength before UV curing, and 1.0 N / 25 mm or less. is there. In the case of an ultraviolet curable pressure sensitive adhesive, it is more preferably 10% or less.

When the pressure-sensitive adhesive is UV curable, an oligomer having a double bond in the molecular chain is used. However, if the molecular weight is small, the cohesive force is low, so that it easily elutes into the etching solution, leading to contamination of the etching solution. Although the elution into the etching solution can be suppressed by adjusting the ratio of the oligomer and the polymer, more preferably, the pressure-sensitive adhesive is mainly composed of a polymer having a double bond in the polymer and does not contain an oligomer. If no oligomer is contained in the main component of the pressure-sensitive adhesive, the low molecular weight component in the pressure-sensitive adhesive is reduced, so that the acid resistance is excellent and elution into the etching solution can be reduced as much as possible.

The surface protective tape whose pressure-sensitive adhesive is pressure sensitive is usually heated at about 50 ° C. when it is peeled off. Peeling can be facilitated by reducing the adhesive strength when heated. For this reason, if the adhesive strength to the SUS280 polished surface at the time of heat peeling at 50 ° C. is 50% or less compared to the adhesive strength at the time of normal peeling (peeling at a normal method (24 ° C.)), it can be easily peeled off Become.

The thickness of the pressure-sensitive adhesive layer is more preferably 20 μm to 40 μm.
By setting it within this range, it is possible to follow the steps of the semiconductor wafer further, no dust intrusion occurs, no edge floating occurs, and the infiltration of the etching solution is avoided. Moreover, cost increase due to being too thick is avoided, and there is no adhesive residue due to cohesive failure.

In the present invention, the main component of the pressure-sensitive adhesive layer 23 is preferably a copolymer of a (meth) acrylic polymer, and the use of the (meth) acrylic polymer makes it easy to control the adhesive force, Since the rate and the like can be controlled, it is possible to reduce contamination due to adhesive residue and organic matter. Examples of the copolymer of (meth) acrylic polymer include a monomer mixture mainly composed of (meth) acrylic acid alkyl ester described in JP-A-2003-82307, and ethylene or propylene containing a radical polymerizable functional group. The main component may be an acrylic emulsion polymer (including latex) obtained by emulsion polymerization (emulsion polymerization) using a nonionic anionic reactive emulsifier having an average oxide addition mole number of 15 or less and a redox polymerization initiator. it can.

The pressure-sensitive adhesive composition is mainly composed of an acrylic emulsion polymer, and an emulsion of (meth) acrylic acid alkyl ester as a main monomer and, if necessary, other monomers copolymerizable with these main monomers. A polymer obtained by polymerization can be used.
Here, the main component means that it exceeds 50% by mass in the total polymer mass of the pressure-sensitive adhesive, preferably 60 to 100% by mass, more preferably 80 to 100% by mass. Moreover, a main monomer means the monomer in which most mass is incorporated among each monomer which comprises a polymer.

Specific examples of (meth) acrylic acid alkyl ester monomers used as the main monomer for the polymerization reaction include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic. Butyl acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, (meth) Examples include isodecyl acrylate. These may be used singly or in combination of two or more. It is preferable to use a mixture of two or more types, and the functions as various pressure-sensitive adhesives can be exhibited by mixing two or more types. It is more preferable to mix three or more kinds, and at least three kinds of methyl (meth) acrylate (methyl acrylate), butyl acrylate (butyl acrylate) and (meth) acrylic acid 2-ethylhexyl (2-ethylhexyl acrylate) are at least combined. It is particularly preferred to polymerize. In particular, the copolymerization of three types of monomers makes it easier to achieve both the ability to follow a step and the non-staining property including adhesive residue.

Further, in addition to the main monomer, various co-polymers can be used for the purpose of stabilizing emulsion particles, improving the adhesion of the pressure-sensitive adhesive layer to the substrate, and improving the initial adhesion to the adherend, as necessary. A polymerizable monomer can be used in combination.

Examples of the copolymerizable monomer include acrylic acid, methacrylic acid, maleic acid, crotonic acid, vinyl acetate, styrene, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N, N-diethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine and the like can be mentioned. These may be used singly or in combination of two or more.

Also, in order to adjust the gel fraction of the pressure-sensitive adhesive layer 23, a polyfunctional monomer component can be copolymerized when the acrylic emulsion copolymer is polymerized. As another method, the gel fraction can be adjusted by mixing a water-dispersible crosslinking agent. As the water dispersible crosslinking agent, an epoxy crosslinking agent is mainly used. It is preferable to polymerize the acrylic emulsion copolymer without using a water-dispersible cross-linking agent, whereby contamination due to the remaining cross-linking agent can be eliminated.

In the pressure-sensitive adhesive layer used in the present invention, the gel fraction in the pressure-sensitive adhesive is not particularly limited, but is preferably 80 to 99%, more preferably 90 to 99%.
The gel fraction in this case is obtained as follows.
A sample is cut into a size of 100 mm × 125 mm to obtain a test piece. The test piece is left in an atmosphere of 23 ° C. and 65% RH for 2 hours, and the mass is measured. Next, after immersing in toluene for 24 hours, the gel is taken out, dried completely, and the mass is measured. The gel fraction is calculated from the mass of the gel after drying and the mass of the adhesive before soaking in toluene.

Examples of the polyfunctional monomer include diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, and neopentyl glycol dimethacrylate. 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Hexameta relay , And divinylbenzene.

A polymerization initiator and a surfactant (emulsifier) are added to the above monomer mixture, and an acrylic emulsion polymer is synthesized using a normal emulsion polymerization method. For emulsion polymerization, any method such as general batch polymerization, continuous dropping polymerization, and divided dropping polymerization can be used, and the method is not particularly limited.

Surfactants include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl Nonionic surfactants such as phenyl ether can be used in combination. Among these surfactants, one or more kinds are used, but preferably two or more kinds of surfactants are used in combination. It is particularly preferable to use a polypropylene glycol compound and polyethylene oxide alkylphenyl ether in combination, whereby organic contamination of the semiconductor wafer can be reduced.

The compounding amount of the surfactant is 0.5 to 10 parts by mass, preferably about 1 to 7 parts by mass with respect to 100 parts by mass of the total monomer mixture. By making the blending amount of the surfactant within this range, the cohesive force of the pressure-sensitive adhesive does not decrease, thereby reducing the amount of contamination on the adherend, and the surface-active agent bleeds to the surface of the pressure-sensitive adhesive layer. Stable emulsification can be maintained without contamination.

As polymerization initiators, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) Azo compounds such as potassium persulfate, persulfates such as ammonium persulfate, peroxide compounds such as benzoyl peroxide and t-butyl hydroperoxide, hydrogen peroxide solution and ascorbic acid, hydrogen peroxide solution And redox polymerization initiators such as ferrous chloride, persulfate and sodium bisulfite.

The polymerization initiator is desirably used in the range of 0.01 to 1.0 part by mass per 100 parts by mass of the total monomer mixture.

Moreover, as one of the manufacturing methods of the (meth) acrylic-type copolymer which is a (meth) acrylic-type polymer, it has a functional group which can react with monomers (1), such as alkyl acrylate ester, and the hardening | curing agent mentioned later. There is a method of copolymerizing the monomer (2) in an organic solvent.

Examples of the monomer (1) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and the like. These may be used singly or in combination of two or more.

Examples of the monomer (2) include acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, maleic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, and methacrylamide. Can be mentioned. These may be used singly or in combination of two or more.

(Meth) acrylic copolymer can be obtained by copolymerizing the above monomers (1) and (2) by a solution polymerization method according to a conventional method.

In the case of an acrylic emulsion polymer, it can be used without a crosslinking agent, but the adhesive strength of a (meth) acrylic copolymer polymerized in a solvent is controlled by further blending a curing agent. A predetermined adhesive strength can be obtained by adjusting the blending amount of the curing agent.

The curing agent is used for adjusting the adhesive force and cohesive force by reacting with the functional group of the (meth) acrylic copolymer. For example, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,3-bis (N, N-diglycidylaminomethyl) toluene, 1,3-bis (N, N-diglycidylaminomethyl) ) Epoxy compounds having two or more epoxy groups in the molecule, such as benzene, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 2,4-tolylene diisocyanate, 2,6-triylene Diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4′-diisocyanate and other isocyanate compounds having two or more isocyanate groups in the molecule, tetramethylol-tri-β- Aziridinyl propionate, trimethylol-tri-β-aziridinyl propionate And aziridine compounds having two or more aziridinyl groups in the molecule such as trimethylolpropane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β- (2-methylaziridine) propionate, etc. It is done.

(Base film)
The base film 20 used in the present invention is a composite base film having a two-layer structure of a high elastic modulus layer and a low elastic modulus layer. The high elastic modulus layer is disposed on the opposite surface (back surface) to the surface on which the pressure-sensitive adhesive layer is applied. The thickness of the composite substrate film is 50 μm to 200 μm, and more preferably 80 μm to 150 μm.
Normally, in the case of a memory device, bonding of a dicing tape or bonding of a dicing die bonding film (DDF) is performed before the surface protective tape is peeled off. On the other hand, in the case of a device that requires an etching process, it is necessary to perform an etching process after grinding, so an in-line apparatus cannot be used, and the thickness is relatively thick, or a support plate is used for etching and back metal processing. Since it may be performed, it mounts on a dicing tape after surface protection tape peeling. Since heat of about 80 ° C. is generally applied when DDF is attached, a base film having heat resistance is essential on the back side of the surface protection tape. When etching while protecting the circuit surface with the surface protection tape, the contact area with the acid is the widest on the back of the base film, so it is essential to have a base film with etching resistance on the back side of the surface protection tape with a certain thickness Become. Further, in order to control the etching rate at that time, the etching solution may be heated, so that heat resistance is often required.

Since it is necessary to provide the above performance, polypropylene (PP) or linear polyethylene (PE) is an essential material in the present invention as the material of the high elastic modulus layer. Polypropylene or linear polyethylene is presumed to have high water resistance due to its small polarity due to its molecular structure, and to be resistant to polar acids. Therefore, even when the ratio of strong acid such as sulfuric acid increases during etching, it is possible to prevent the penetration of acid into the semiconductor wafer. This effect is particularly noticeable when the proportion of sulfuric acid is large. On the other hand, a highly polar PET film or the like allows the acid to enter.
In addition, when a high elastic modulus layer such as PP or linear PE is used on the back surface of the base film, the warping performance after grinding deteriorates. Since the warpage increases as the constituent ratio of the high elastic modulus layer increases, the ratio between the thickness of the high elastic modulus layer and the low elastic modulus layer (high elastic modulus) The thickness of the layer: the thickness of the low elastic modulus layer) is 1: 9 to 5: 5 in the present invention. When the ratio of the high elastic modulus layer exceeds 5, warpage increases and a transport error or the like occurs. On the other hand, if it is less than 1, heat resistance and etching resistance are insufficient.
The thickness of the high elastic modulus layer is 10 μm or more, and more preferably 10 μm to 50 μm.

Furthermore, the polypropylene used is preferably stretched. This is because the strength is increased by stretching. As the stretching, biaxial stretching is preferable, and since the residual stress during film formation can be relaxed by stretching in both directions, the amount of warpage after grinding the back surface of the semiconductor wafer can be reduced, and the conveying process after thin film grinding Even in this case, it is possible to carry without causing an error. This stretch-treated polypropylene can be manufactured by annealing or the like, but as a commercial product, alpha-in (trade name, manufactured by Oji Special Paper Co., Ltd.), OP-U1 (trade name, manufactured by Mitsui Chemicals, Inc.), Pyrene (registered trademark) , Toyobo Co., Ltd.) and other films are available.

The linear polyethylene refers to a polymer obtained by polymerizing ethylene linearly, and there are mainly two types of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE). The linear polyethylene is produced by an intermediate pressure method or a low pressure method, and examples of the low pressure method include a Ziegler method. The Ziegler method uses a Ziegler-Natta catalyst, triethylaluminum-titanium tetrachloride solid composite, as a catalyst, paraffin, naphthene, or lower aliphatic hydrocarbon as a solvent, while applying ethylene at normal pressure or several atmospheric pressures. The solution is blown into a solvent and polymerized at a solution temperature of about 60 to 100 ° C. The obtained slurry polymer is then washed with water to separate and recover the solvent and dried. The medium pressure method includes the Philips method and the standard method. In the Philips method, ethylene is polymerized in an environment of 30 to 40 atmospheres and 100 to 175 ° C using silica-alumina / hexavalent chromium as a catalyst and paraffin, naphthene or hexane as a solvent. To do. The standard method uses gamma-alumina / molybdenum oxide as a catalyst and polymerizes in an environment of 15 to 150 atmospheres and 150 to 250 ° C. Thereafter, the residual monomer is separated, and after cooling, the solvent is recovered by filtration.

The density (g / cm ³ ) of these linear polyethylenes is preferably from 0.910 to 0.970, more preferably from 0.945 to 0.969. By setting the density within this range, the material does not become brittle, and therefore deterioration of manufacturability and film properties can be avoided. Moreover, acid resistance can also be maintained. Such polyethylene can be produced by, for example, extruding a linear polymerized polyethylene resin produced by Asahi Kasei Engineering, Nippon Polyethylene, Tosoh, Nihon Unicar, and Prime Polymer with a T-die. . In addition, the formed film can be biaxially stretched by annealing. The linear polyethylene used in the present invention is preferably biaxially stretched.

The melt mass flow rate (MFR) of linear polyethylene is preferably 10 g / 10 min or less. By setting the MFR to 10 g / 10 min or less, the high molecular weight component having advanced crosslinking increases, or the molecular weight distribution is narrow and the low molecular weight component is also small, thereby reducing the possibility of being attacked by acid during etching. . Also, the thickness accuracy during film formation is increased.

For the low elastic modulus layer of the present invention, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 20% by mass and an MFR of 1 to 10 g / 10 min is used. If the low elastic modulus layer described in JP-A-2004-186429 is used, the warpage and the thickness accuracy after grinding are deteriorated, and in the worst case, the semiconductor wafer is cracked.
By using an ethylene-vinyl acetate copolymer, it is possible to achieve a good semiconductor wafer thickness accuracy even after grinding, and it is optimal as a material for thin film grinding because it suppresses warpage.
The vinyl acetate content of the ethylene-vinyl acetate copolymer is 5 to 20% by mass as described above. However, as this content decreases, the warpage deteriorates because it approaches normal polyethylene. When it exceeds 20 mass%, since melting | fusing point is too low, blocking will generate | occur | produce at the time of film forming of a base film, or thickness accuracy will deteriorate.

The MFR of the ethylene-vinyl acetate copolymer is 0.8 to 10 g / 10 min. However, if the MFR is less than 0.8 g / 10 min, it is difficult to extrude and deteriorates the thickness accuracy, and conversely exceeds 10 g / 10 min. The resin tends to stay in the screw during extrusion, and resin burns and fish eyes are generated.
The high elastic modulus layer made of the linear polyethylene or ethylene-vinyl acetate copolymer of the multilayer substrate film is desirably formed into a film without using other materials such as an adhesive. Preferably, the influence of the warp due to the stress applied to the elution and bonding of the adhesive component to the etching solution can be suppressed by extruding simultaneously with the low elastic modulus layer. As a method for molding without an adhesive, a method of extruding at the same time using a screw and laminating by cooling at once with a cooling roll can be used.

In order to form the above-mentioned pressure-sensitive adhesive layer on the base film of the present invention, at least one type of pressure-sensitive adhesive may be applied to at least one side of the base film by any method. As described above, the thickness of the pressure-sensitive adhesive layer is preferably 10 to 50 μm. Moreover, you may provide intermediate | middle layers, such as a primer layer, as needed between a base film and an adhesive layer.

Further, if necessary, a synthetic resin film usually used as a separator for protecting the pressure-sensitive adhesive layer may be stuck on the pressure-sensitive adhesive layer side until it is put to practical use.

The tack force of the adhesive tape for protecting a semiconductor wafer surface of the present invention is preferably 60 to 450 kPa, more preferably 60 to 200 kPa.
By adjusting the tack force within the above range, preferably 60 to 200 kPa, the wafer edge portion is prevented from being lifted, and the dust and the etchant are less likely to enter. In addition, since it will be hard to peel when it contacts the roll of a bonding machine when tack force is enlarged too much, a bonding error will be caused frequently and workability will be worsened.
Here, the tack force is measured by pushing a 3 mmφ cylindrical probe at a speed of 30 mm / min with a probe-type tacking tester manufactured by Reska Co., and holding the pulling load at 100 g for 1 second and then pulling it up at a speed of 600 mm / min. Can do.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

<Example 1>
Thickness of an ethylene-vinyl acetate copolymer (EVA) having a thickness of 10 μm of polypropylene (PP) having a density of 0.910 g / cm ³ , a vinyl acetate content (VA content) of 10% by mass, and an MFR of 9 g / 10 min. Was formed into a film by co-extrusion, and a multilayer substrate film (1) consisting of two layers having a total thickness of 100 μm was formed. In addition, corona treatment was performed on the EVA surface side during film formation to improve adhesion with the adhesive.
A polyoxyethylene alkylphenyl ether compound and a polypropylene glycol compound to which an allyl group was added as a surfactant were added to deionized pure water, and ammonium persulfate was added as a polymerization initiator and stirred while heating. Next, 17 parts by weight of methyl methacrylate, 40 parts by weight of butyl acrylate, 41 parts by weight of 2-ethylhexyl acrylate, 2 parts by weight of glycidyl methacrylate are added dropwise to the stirring solution, and the polymerization is continued while stirring to prepare an acrylic emulsion adhesive. Composition A was obtained.
The pressure-sensitive adhesive composition A was applied on a 25 μm release agent-coated PET separator so that the thickness after drying was 30 μm, and was dried in a drying furnace at 120 ° C. to form a multilayer substrate film (1). The pressure-sensitive adhesive tape for protecting the surface of a semiconductor wafer with a separator having a total thickness of 155 μm was prepared by laminating by laminating on the EVA side.

<Example 2>
Treffan (registered trademark) 2578 (trade name, manufactured by Toray Industries, Inc.), which is a 40 μm-thick polypropylene film (PP) having a density of 0.910 g / cm ³ subjected to biaxial stretching, and a vinyl acetate content of 20% by mass, A multi-layer base material with a total thickness of 80 μm is obtained by dry laminating a base film with an MFR 0.8 g / 10 min ethylene-vinyl acetate copolymer (EVA) extruded to a thickness of 40 μm and corona-treated on both sides with an adhesive. A film (2) was obtained.
In the same manner as in Example 1, the pressure-sensitive adhesive composition A was applied to a 25 μm-thick release agent-coated PET separator so that the thickness after drying was 50 μm, and was applied to the EVA side of the multilayer substrate film (2). A pressure-sensitive adhesive tape for protecting the surface of a semiconductor wafer with a separator having a total thickness of 155 μm was prepared by bonding.

<Example 3>
A high density polyethylene (HDPE) having a density of 0.964 g / cm ³ and MFR of 15 g / 10 min was formed into a film having a thickness of 20 μm by extrusion, and then annealed. An ethylene-vinyl acetate copolymer (EVA) having a vinyl acetate content of 6 mass% and an MFR of 2.5 g / 10 min was extruded to obtain an EVA film having a thickness of 80 μm. The HDPE film and EVA film were dry laminated using an adhesive to obtain a multilayer substrate film (3) having a total thickness of 100 μm. Thereafter, corona treatment was performed on the EVA surface in order to improve the adhesion with the adhesive.
ATR-340 (manufactured by Seiden Chemical Co., Ltd.), an acrylic polymer, is blended in an amount of 0.8 parts by mass of adduct isocyanate cross-linking agent Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) and ethyl acetate. The pressure-sensitive adhesive composition B was obtained by adjusting the concentration.
Apply the pressure-sensitive adhesive composition B onto a 25 μm PET separator so that the thickness after drying is 20 μm, dry it in a drying oven at 120 ° C., and laminate it to the multilayer substrate film (3). And a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 155 μm was produced.

<Example 4>
Polypropylene (PP) having a density of 0.910 g / cm ³ is 33 μm thick, and an ethylene-vinyl acetate copolymer (EVA) having a vinyl acetate content of 5 mass% and MFR of 2.8 g / 10 min is co-extruded at a thickness of 77 μm. Film formation was performed to form a multilayer substrate film (4) composed of two layers having a total thickness of 110 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the EVA surface.
As an energy ray curable copolymer, a 25% ethyl acetate solution of an acrylic copolymer having a mass average molecular weight of 700,000 consisting of 65 parts by mass of butyl acrylate, 30 parts by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of methyl methacrylate 100 Mass parts and 8 parts by mass of methacryloyloxyethyl isocyanate (80 equivalents with respect to 100 equivalents of the functional group of the acrylic copolymer) were reacted to obtain the energy ray curable acrylic copolymer. For 100 parts by mass of this acrylic copolymer, 2 parts by mass of an isocyanate-based crosslinking agent Coronate L (trade name, manufactured by Nippon Polyurethane) and a photopolymerization initiator Irgacure 184 (trade name, manufactured by Ciba Japan) are used. 5 mass parts was mix | blended, the density | concentration was adjusted with ethyl acetate, and the ultraviolet curable adhesive composition C was obtained.
Apply the pressure-sensitive adhesive composition C on a 25 μm PET separator so that the thickness after drying is 20 μm, dry it in a drying oven at 120 ° C., and laminate it on the multilayer substrate film (4). And a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 155 μm was produced.

<Example 5>
A linear low-density polyethylene (LLDPE) GA701 (Sumikasen-L manufactured by Sumitomo Chemical Co., Ltd.) having a density of 0.923 g / cm ³ and MFR of 8 g / 10 min is 15 μm thick, has a vinyl acetate content of 10% by mass and an MFR of 10 g / 10 min. An ethylene-vinyl acetate copolymer (EVA) was formed into a film with a thickness of 135 μm by coextrusion to form a multilayer substrate film (5) consisting of two layers with a total thickness of 150 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the EVA surface.
Acrylic polymer Polysic 410-SA (manufactured by Sanyo Chemical Co., Ltd.) is blended with 100 parts by mass of adduct isocyanate cross-linking agent Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.), and acetic acid. The pressure-sensitive adhesive composition D was obtained by adjusting the concentration with ethyl.
Apply the pressure-sensitive adhesive composition D on a 25 μm PET separator so that the thickness after drying is 30 μm, dry it in a drying oven at 120 ° C., and laminate it on the multilayer substrate film (5). And a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 205 μm was prepared.

<Example 6>
A high density polyethylene (HDPE) having a density of 0.965 g / cm ³ and an MFR of 5 g / 10 min is 20 μm thick, a vinyl acetate content of 19% by mass, and an ethylene-vinyl acetate copolymer (EVA) having an MFR of 2.5 g / 10 min is 180 μm. A film was formed by coextrusion at a thickness to form a multilayer substrate film (6) consisting of two layers having a total thickness of 200 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the EVA surface.
100 parts by mass of S-1605 (trade name, manufactured by Toa Gosei Co., Ltd.), an acrylic polymer, and 2.2 parts by mass of adduct isocyanate cross-linking agent Coronate L (trade name, manufactured by Nippon Polyurethane) The pressure-sensitive adhesive composition E was obtained by adjusting the concentration with ethyl acetate.
Apply the pressure-sensitive adhesive composition E on a 25 μm PET separator so that the thickness after drying is 10 μm, dry it in a drying oven at 120 ° C., and laminate it on the multilayer substrate film (6). And a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 235 μm was produced.

<Example 7>
High density polyethylene (HDPE) having a density of 0.952 g / cm ³ and MFR of 21 g / 10 min is 20 μm thick, vinyl acetate content is 14% by mass, MFR 1.3 g / 10 min of ethylene-vinyl acetate copolymer (EVA) is 30 μm. A film was formed by coextrusion at a thickness to form a multilayer substrate film (7) consisting of two layers having a total thickness of 50 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the EVA surface.
Isocyanate-based crosslinking agent Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) with respect to 100 parts by mass of an acrylic base resin having a mass average molecular weight of 700,000, which is a copolymer of 2-ethylhexyl acrylate, methyl acrylate and 2-hydroxyethyl acrylate 4 parts by weight, 150 parts by weight of tetramethylolmethane tetraacrylate having a photopolymerizable carbon-carbon double bond as an oligomer, and 5 parts by weight of a photopolymerization initiator Irgacure 184 (trade name, manufactured by Ciba Japan) are mixed with ethyl acetate. The pressure-sensitive adhesive composition F was obtained after adjusting the concentration.
Apply the pressure-sensitive adhesive composition F on a 25 μm PET separator so that the thickness after drying is 30 μm, dry it in a drying furnace at 120 ° C., and laminate it on the multilayer substrate film (7). A separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 105 μm was prepared.

<Comparative Example 1>
Acrylate ASTR-228SN (manufactured by Nippon Shokubai Co., Ltd.), which is an acrylic polymer, is blended with 100 parts by mass of an isocyanate-based crosslinking agent D-90 (trade name, manufactured by Soken Chemical Co., Ltd.) in an amount of 1.5 parts by mass. The pressure-sensitive adhesive composition G was obtained by adjusting the concentration with ethyl.
The adhesive composition G is applied onto a 25 μm PET separator so that the thickness after drying is 40 μm, dried in a drying oven at 120 ° C., and laminated to a polyethylene terephthalate (PET) film having a thickness of 50 μm. Thus, an adhesive tape for protecting the surface of a semiconductor wafer with a separator having a total thickness of 115 μm was produced.

<Comparative example 2>
An ethylene-vinyl acetate copolymer (EVA) film with a vinyl acetate content of 5% by mass is formed into a single-layer substrate film (8) having a thickness of 50 μm by extrusion, and the surface to which the adhesive is applied is subjected to corona treatment. went.
100 parts by mass of GS Stack P-1000 (trade name, manufactured by Sanyo Kasei Co., Ltd.), an acrylic polymer, and 1 part by mass of adduct isocyanate crosslinker Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) and epoxy 0.1 part by mass of a system curing agent TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.) was blended, and the concentration was adjusted with ethyl acetate to obtain an adhesive composition H.
Apply the pressure-sensitive adhesive composition H onto a 25 μm PET separator so that the thickness after drying is 10 μm, dry it in a drying oven at 120 ° C., and bond and laminate to a single-layer substrate film (8). And a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 85 μm was prepared.

<Comparative Example 3>
Polypropylene (PP) with a density of 0.910 g / cm ³ is 5 μm thick, vinyl acetate content 19 mass%, MFR 2.5 g / 10 min ethylene-vinyl acetate copolymer (EVA) is 75 μm thick by coextrusion. Film formation was performed to form a multilayer substrate film (9) consisting of two layers having a total thickness of 80 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the EVA surface.
Two isocyanate crosslinkers Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) are added to 100 parts by mass of an acrylic base resin having a molecular weight of 300,000 which is a copolymer of 2-ethylhexyl acrylate, butyl acrylate and 2-hydroxyethyl acrylate. 1 part by mass, 150 parts by mass of tetramethylolmethane tetraacrylate having a photopolymerizable carbon-carbon double bond as an oligomer, and 5 parts by mass of photopolymerization initiator Irgacure 184 (trade name, manufactured by Ciba Japan) are mixed with ethyl acetate. The pressure-sensitive adhesive composition I was obtained by adjusting the concentration.
Apply the pressure-sensitive adhesive composition I on a 25 μm PET separator so that the thickness after drying is 55 μm, dry it in a drying furnace at 120 ° C., and laminate it on the multilayer substrate film (9). The separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 160 μm was prepared.

<Comparative Example 4>
Polypropylene (PP) was extruded to obtain a single layer substrate film (10) having a thickness of 110 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the surface to which the adhesive is bonded.
100 parts by mass of S-1605 (trade name, manufactured by Toa Gosei Co., Ltd.), an acrylic polymer, and 2.2 parts by mass of adduct isocyanate cross-linking agent Coronate L (trade name, manufactured by Nippon Polyurethane) The pressure-sensitive adhesive composition E was obtained by adjusting the concentration with ethyl acetate.
Apply the pressure-sensitive adhesive composition E on a 25 μm PET separator so that the thickness after drying is 5 μm, dry it in a drying oven at 120 ° C., and bond and laminate to a single-layer substrate film (10). And a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 140 μm was prepared.

<Comparative Example 5>
High density polyethylene (HDPE) having a density of 0.952 g / cm ³ and MFR of 21 g / 10 min is 198 μm thick, vinyl acetate content is 6 mass%, MFR 2.5 g / 10 min of ethylene-vinyl acetate copolymer (EVA) is 22 μm. A film was formed by coextrusion at a thickness to form a multilayer substrate film (11) consisting of two layers having a total thickness of 220 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the EVA surface.
100 parts by mass of acrylic polymer S-1605 (manufactured by Toa Gosei Co., Ltd.) and 0.5 parts by mass of adduct isocyanate cross-linking agent Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) are blended into ethyl acetate. The pressure-sensitive adhesive composition J was obtained after adjusting the concentration.
The pressure-sensitive adhesive composition J was applied onto a 50 μm PET separator so that the thickness after drying was 90 μm, dried in a drying furnace at 120 ° C., and bonded to the EVA side of the multilayer substrate film (11). By laminating, an adhesive tape for protecting the surface of a semiconductor wafer with a separator having a total thickness of 335 μm was produced.

<Comparative Example 6>
100 parts by mass of the trade name GS Stack P-1000 (manufactured by Sanyo Chemical Co., Ltd.), an acrylic polymer, and 0.5 parts by mass of adduct isocyanate crosslinker Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) And 3.0 parts by mass of an epoxy curing agent TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the concentration was adjusted with ethyl acetate to obtain an adhesive composition K.
A pressure-sensitive adhesive composition K was applied to a 25 μm PET separator so that the thickness after drying was 15 μm, dried in a drying oven at 120 ° C., and a single layer substrate film of polyethylene terephthalate (PET) having a thickness of 50 μm. By laminating by bonding to (12), a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 90 μm was produced.

<Comparative Example 7>
High density polyethylene (HDPE) having a density of 0.965 g / cm ³ and MFR of 5 g / 10 min at a thickness of 20 μm, an ethylene-vinyl acetate copolymer (EVA) having a vinyl acetate content of 30% by mass and MFR of 32 g / 10 min at an thickness of 80 μm. Film formation was carried out by coextrusion, and an attempt was made to form a multilayer substrate film (12) consisting of two layers with a total thickness of 200 μm, but the EVA layer was strongly sticky and adhered to a roll or the like, making it a film. could not.

<Comparative Example 8>
High density polyethylene (HDPE) having a density of 0.965 g / cm ³ and MFR of 5 g / 10 min is 108 μm thick, vinyl acetate content is 6% by mass, and an ethylene-vinyl acetate copolymer (EVA) having an MFR of 2.5 g / 10 min is 72 μm. A film was formed by coextrusion at a thickness to form a multilayer substrate film (13) consisting of two layers having a total thickness of 180 μm. Then, the adhesiveness with an adhesive was improved by performing a corona treatment on the EVA surface.
As an energy ray curable copolymer, a 25% ethyl acetate solution of an acrylic copolymer having a mass average molecular weight of 700,000 consisting of 65 parts by mass of butyl acrylate, 30 parts by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of methyl methacrylate 100 Mass parts and 8 parts by mass of methacryloyloxyethyl isocyanate (80 equivalents with respect to 100 equivalents of the functional group of the acrylic copolymer) were reacted to obtain the energy ray curable acrylic copolymer. For 100 parts by mass of this acrylic copolymer, 2 parts by mass of an isocyanate-based crosslinking agent Coronate L (trade name, manufactured by Nippon Polyurethane) and a photopolymerization initiator Irgacure 184 (trade name, manufactured by Ciba Japan) are used. 5 mass parts was mix | blended, the density | concentration was adjusted with ethyl acetate, and the ultraviolet curable adhesive composition C was obtained.
Apply the pressure-sensitive adhesive composition C on a 25 μm PET separator so that the thickness after drying is 20 μm, dry it in a drying oven at 120 ° C., and laminate it on the multilayer substrate film (13). And a separator-coated semiconductor wafer surface protecting adhesive tape having a total thickness of 225 μm was produced.

The following tests were conducted on the semiconductor wafer surface protecting adhesive tapes produced in the above examples and comparative examples, and their performance was evaluated. The evaluation results are shown in Tables 1 and 2 below.

1. Grindability test Using DR8500II (trade name) manufactured by Nitto Seiki Co., Ltd. as a pasting machine, a polyimide film having a thickness of about 10 μm is formed on a 725 μm thick 8-inch semiconductor wafer, and further a width of about 200 μm and a depth of about 5 μm. The semiconductor wafer, in which the scribe lines are formed in a grid pattern at intervals of about 1 mm, is further subjected to plasma etching treatment, and the semiconductor wafer surface protective adhesive tape produced in the examples and comparative examples is applied to the semiconductor wafer whose surface has been modified. Combined. Thereafter, 25 semiconductor wafers were each polished to a thickness of 100 μm using a grinder having an inline mechanism (DFG8760 (trade name) manufactured by DISCO Corporation), and evaluated according to the following criteria.

(Thin film grindability evaluation criteria)
There were almost no edge cracks and all 25 semiconductor wafers could be ground: A
Although some edge cracks were observed, the wafers could be ground without cracks, or 25 semiconductor wafers had 1 to 2 cracks: B
Three or more semiconductor wafers broken: C

(Dust intrusion evaluation criteria)
Dust or grinding water did not enter the scribe line: A
Dust or grinding water entering the scribe line: C

(Curve evaluation criteria)
A conveyance error did not occur at all, and the amount of warpage was less than 15 mm: A
No conveyance error occurred or less than 10%, and the amount of warpage was 15 mm or more: B
Conveyance error of 10% or more: C

2. Evaluation of peelability A semiconductor wafer ground to a thickness of 100 μm in a grinding experiment was subjected to a peel test using a mounter RAD2700 having an inline mechanism. At the time of peeling, the surface protecting adhesive tape to which the pressure-sensitive adhesive is applied is heated and peeled at 50 ° C., and the surface protecting adhesive tape to which the ultraviolet curable adhesive is applied is irradiated with ultraviolet rays of 500 mJ. After the test, the ultraviolet curable pressure sensitive adhesive was heated and peeled at 24 ° C., and the pressure sensitive pressure sensitive adhesive was evaluated at the following criteria.
All that can be peeled as it is: A
Peeling error or things that could not be peeled: C

3. Evaluation of adhesive residue The surface of the semiconductor wafer that was peeled off in a peeling experiment was observed, and the presence or absence of adhesive residue was evaluated according to the following criteria.
No adhesive residue: A
With adhesive residue: C

4). SUS # 280 Adhesive Strength Three test pieces having a width of 25 mm and a length of 300 mm were collected from the semiconductor wafer surface protecting adhesive tapes of the examples and comparative examples, and the test piece 1 was subjected to JIS R by the method shown in FIG. JIS G 4305 finished with 280 No. 280 water-resistant abrasive paper specified in 6253, JIS G 4305 thickness of 1.5 mm to 2.0 mm thick SUS steel plate 2 applied with 3 rounds of pressure on the SUS steel plate 2 and allowed to stand for 1 hour before measurement The adhesive strength was measured using a tensile tester 3 conforming to JIS B 7721 whose value falls within the range of 15 to 85% of the capacity. In the figure, the arrow indicates the tensile direction. The measurement is performed by a 180-degree peeling method, and the tensile speed at this time is 300 mm / min.

5. Adhesive strength of SUS # 280 for heat peeling Adhesive strength when peeling was performed while heating to 50 ° C. in the same procedure as described above. In addition, about the ultraviolet curable adhesive, after irradiating ultraviolet rays with an irradiation amount of 500 mJ, the ultraviolet curable adhesive was heated and peeled at 24 ° C. and the pressure sensitive adhesive was heated at 50 ° C.

6). Etching Evaluation Sulfuric acid: nitric acid: hydrofluoric acid was mixed at a volume ratio of 85: 13: 2 to prepare an etching solution.
(Etching solution penetration experiment)
The mirror wafer on which a scribe line having the same surface shape as that used in the grinding experiment was bonded to the surface protective adhesive tape created in Examples and Comparative Examples using DR8500II (trade name) manufactured by Nitto Seiki Co., Ltd. It was. The wafer with surface protection was immersed in the blended etching solution at 30 ° C., the back surface of the wafer was etched for 15 minutes, and evaluated according to the following criteria.
Etching solution did not enter: A
Etching solution entered from scribe line or substrate surface: C

7). Substrate film acid resistance experiment A pH test paper on a 6-inch mirror wafer was placed, and a surface protective adhesive tape created in Examples and Comparative Examples was applied using DR8500II (trade name) manufactured by Nitto Seiki Co., Ltd. The etching solution blended on the pH test paper was dropped, left at room temperature for 30 minutes, and evaluated according to the following criteria.
No change in pH test paper color: A
Changed color of pH test paper: C

8). Tack test Using a tacking tester (trade name: TACII, manufactured by Resca), a 3 mmφ cylindrical probe was pushed at a speed of 30 mm / min into the back side of the base film of the test piece (the side opposite to the adhesive-coated surface). The load when pulling up at a speed of 600 mm / min after holding for 1 second with a stop load of 100 g was measured to determine the tack force.

In addition, “layer ratio (high elastic layer: low elastic layer)” in the following Tables 1 and 2 is a ratio of the thicknesses of the high elastic modulus layer and the low elastic modulus layer.

As shown in Tables 1 and 2, in Examples 1 to 7, all of the polyimide film-modified wafers ground into thin films could be peeled off, no adhesive residue was observed, and no intrusion of etching solution was observed. On the other hand, in Comparative Examples 1 to 8, cracking occurred during thin film grinding, adhesive residue, peeling failure, dust intrusion, infiltration of etching liquid, or penetration of etching liquid into the surface of the semiconductor wafer through the base film. It was. Specifically, in Comparative Examples 1, 2, and 3, the acid resistance of the base film was poor, the etching solution entered, and did not act as a base film. Moreover, since the thickness of the pressure-sensitive adhesive layer was large, in Comparative Examples 3 and 5, the surface edge of the semiconductor wafer was contaminated with the etching liquid because of the elution of the pressure-sensitive adhesive into the etching liquid. Furthermore, in Comparative Examples 3 and 5, since it was eroded by the etchant, adhesive residue was generated at the edge portion. In addition, in the comparative example 3, the ultraviolet curable pressure-sensitive adhesive had a heavy peeling at the end portion, which resulted in poor peeling because the photoreaction initiator contaminated with the etching solution was decomposed. In Comparative Example 4, since the thickness of the pressure-sensitive adhesive was as very thin as 5 μm, dust intrusion and etching solution intrusion occurred. In Comparative Example 5, since the thickness of the pressure-sensitive adhesive layer is very thick as 90 μm, adhesive residue due to insufficient cohesive force is generated at the time of peeling, and since it is highly adhesive even after heat peeling, a tape peeling failure occurs. It was. In Comparative Example 6, the acid resistance of the base film to the etching solution was poor, the holding power and grindability of the semiconductor wafer were completely poor, and the function of the adhesive tape was not achieved. In Comparative Example 7, the base film could not be formed. Since Comparative Example 8 has a large amount of warpage, a transport error frequently occurs, and a problem that the semiconductor wafer falls and breaks also occurs.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2012-062725 filed in Japan on March 19, 2012 and Japanese Patent Application No. 2012-278733 filed on December 20, 2012 in Japan. Which are hereby incorporated by reference herein as part of their description.

DESCRIPTION OF SYMBOLS 1 Adhesive tape test piece 2 SUS steel plate 3 Tensile tester 20 Base film 21 Back surface 22 Front surface 23 Adhesive layer

Claims

A pressure-sensitive adhesive tape for protecting a semiconductor wafer surface having a pressure-sensitive adhesive layer on a base film,
The base film is a composite base film having a total thickness of 50 μm to 200 μm and comprising a high elastic modulus layer and a low elastic modulus layer, and a ratio of thicknesses of the high elastic modulus layer and the low elastic modulus layer ( The thickness of the high elastic modulus layer: the thickness of the low elastic modulus layer) is in the range of 1: 9 to 5: 5,
The high elastic modulus layer is disposed on the back surface of the pressure-sensitive adhesive layer (the surface opposite to the surface on which the pressure-sensitive adhesive layer of the base film is applied), and has a thickness of 10 μm or more made of polypropylene or linear polyethylene Layer,
The low elastic modulus layer comprises an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 20% by mass and an MFR of 0.8 to 10 g / 10 min.
The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape for protecting a semiconductor wafer surface is 10 μm to 50 μm. A pressure-sensitive adhesive tape for protecting a semiconductor wafer, characterized by being not more than 0.0 N / 25 mm and not more than 50% of the adhesive strength when not heated or not irradiated with ultraviolet rays.
2. The semiconductor according to claim 1, wherein the resin of the high elastic modulus layer is a linear polyethylene having a density of 0.910 to 0.970 g / cm 3 and an MFR of 10 g / 10 min or less. Adhesive tape for wafer surface protection.
The adhesive for semiconductor wafer surface protection according to claim 1 or 2, wherein the high elastic modulus layer and the low elastic modulus layer of the base film are laminated without using any other material of an adhesive. tape.
The adhesive tape for protecting a semiconductor wafer surface according to any one of claims 1 to 3, wherein the adhesive layer is a pressure-sensitive adhesive and is used in a semiconductor processing process including an etching step.
The adhesive tape for protecting a semiconductor wafer surface according to any one of claims 1 to 4, wherein the base film polypropylene or linear polyethylene is biaxially stretched.
The adhesive tape for protecting a semiconductor wafer surface according to any one of claims 1 to 5, wherein the tack force is 60 to 200 kPa.
The semiconductor wafer surface protecting adhesive tape according to any one of claims 1 to 6, wherein the adhesive layer is an emulsion adhesive.
8. The semiconductor wafer surface protecting pressure-sensitive adhesive tape according to claim 7, wherein the emulsion-based pressure-sensitive adhesive layer does not contain a water-dispersible isocyanate crosslinking agent.