Base material and adhesive tape using the same

Abstract: A base material (3) for an adhesive tape has a film layer (1) and a barrier layer (2) on its surface. An adhesive tape (5) includes also an adhesive layer (4) on the barrier layer (2). Such adhesive tapes have neither fish-eyes nor contaminating foreign substances on their surfaces, so that accuracy of thickness is improved and contamination of materials adhered to the adhesive layer (4) is avoided.

Description: The present invention relates to an adhesive tape to be used in the process of precision-machining of an optical structural element such as a lens, a semiconductor structural element such as a silicon wafer, or the like. The present invention also relates to an adhesive tape having such a particular base material. Heretofore, adhesive tapes have been used in the fields of optical industry, semiconductor industry, and so on, for manufacturing structural elements that require precision-machining. Generally, the adhesive tape for surface protection of a semiconductor wafer can be prepared by the process including the steps of: melting a thermoplastic resin; forming a film-shaped base material as a base sheet by casting the melted thermoplastic resin by the use of a T-die, a blow-extrusion, a calender, or the like; and applying an adhesive agent on at least one surface of the base sheet. The adhesive tape thus obtained is typically used for holding a semiconductor wafer in place during the step of grinding a back side of the wafer and also the steps of dicing and isolating the wafer into pieces. At first, we will explain the example of using the adhesive tape in the process of grinding a back side of a semiconductor wafer that has a front side on which a predetermined pattern is formed (i.e. a step of back-side grinding). At the time of grinding the back side of the wafer, the back-side of the wafer is continuously rinsed by running pure water to remove scattered or fragmented remains (i.e., debris) and to reduce heat generated by the grinding. In this case, therefore, an adhesive tape is applied on the front side of the wafer to protect the pattern formed thereon from the grinding. At the time of performing the steps of dicing and isolating the semiconductor wafer into pieces, an adhesive tape is applied on the back side of the wafer, so that the wafer on which the adhesive tape is being adhered is subjected into each of the steps of dicing, washing, drying, expanding, pick-upping, and mounting, successively. These steps require that the adhesive tape should have the properties of, for example without remaining any part of the adhesive agent on a wafer or a chip when the adhesive tape is removed after the step of back-side grinding or the steps of dicing and isolating. For solving this problem, several improvements have been disclosed in patent documents including Japanese Patent Application Laying-open'No. 62-153376 (1987) and Japanese Patent Application Publication No. 5-77284 (1993). An adhesive sheet disclosed in Japanese Patent Application Laying-open No. 62-153376 (1987) comprises an adhesive that contains urethane acrylate oligomer (m.w. 3,000-10,000) as a radiation-induced polymerized compound and a base sheet on which the adhesive is applied. Therefore, an adhesive strength of the adhesive sheet is sufficiently decreased by an effect of irradiating it with ultraviolet rays or the like in the step of pick-upping after dicing the semiconductor wafer. Thus, the adhesive agent does not remain on the back side of the wafer chip. On the other hand, an adhesive tape disclosed in Japanese Patent Application Publication No. 5-77284 (1993) comprises a water-swelling type adhesive agent as an adhesive layer applied on a surface of a base sheet. In this case, therefore, it becomes to possible to remove the adhesive agent attached on the wafer's surface by running water after the grinding step. Each of the adhesive tapes described above uses the base material which is prepared as a film-shaped material by melting a thermoplastic resin such as vinyl chloride or polypropylene and casting the melted thermoplastic resin by the use of a T-die, a blow-extrusion, a calender, or the like. In most cases, the base material to be used has a thickness of 50µm or more in terms of wafer-protection and workability. During the process of forming the base material into a film, however, projections are sparsely formed on a surface of the base material as a result of mixing undesired foreign substances into the material or the existence of insoluble ingredients of its resin component or the like. Each of those projections are in the shape of like a fish's eye with a height of about 10 to 50µm (which is referred as "a fish-eye" in the following description). Therefore, the fish-eye acts as a center of spreading the breakage of a silicon wafer at the time of grinding the back side of the wafer. In this case, furthermore, another problem that the fish-eye acts as a center of flying a chip off comes up at the time of dicing and isolating the chip. The generation of fish-eyes may be under control if the base material is of less than 50µm in thickness. However, such a thin film cannot attain the capability of wafer-protection and leads to poor workability. For solving these disadvantages, Japanese Patent Application laying-open No. 9-253964 (1997) discloses a base material for an adhesive tape. The base material is formed by casting a liquid radiation-cured resin comprising a mixture of urethane acrylate oligomer and reactive diluted monomer followed by the step of curing the resin by irradiating with a radiation. However, one of the drawbacks of forming an adhesive tape by directly applying an adhesive layer on a film layer of the base material is to pollute a adherend (e.g., a semiconductor wafer) with a residual adhesive (the so-called "particle") which is remained on a surface of the adherend when the adhesive tape is removed from the adherend. The present inventors and their coworkers have considered that the cause of the particle (i.e., the residual adhesive of the above adhesive agent on the adherend) is a bleeding of unacceptable ingredients from the film layer to the adhesive layer. The unacceptable ingredients have a low molecular weight and are comprised in the radiation-cured resin that forms the film layer of the base material. Eventually, they find that the solution to the above problem lies in using a base material in which a barrier layer is formed on the film layer. The barrier layer is responsible for preventing the bleeding from the film layer to the adhesive layer. Accordingly, it is an object of the present invention to provide an adhesive tape having the excellent properties of improving the contamination of a adherend with an adhesive as described above and providing the accuracy of thickness, in which fish-eyes and foreign substances are not included. The present invention provides an adhesive tape comprising: a base material having a film layer which is formed by curing a mixture of urethane (meth) acrylate oligomer and reactive-diluted monomer by irradiating it with a radiation, and a barrier layer which is formed on at least one surface of the film layer; and an adhesive layer which is formed on at least one surface of the barrier layer. The barrier layer may have a thickness of 0.1µm to 40µm. Here, the reactive-diluted monomer may be a monomer having a ring structure. The monomer having a ring structure may be a monomer selected from a group consisting of: cycloaliphatic compounds, aromatic compounds, and heterocyclic compounds. The barrier layer may have a thickness of 0.1µm to 40µm. By forming a barrier layer on a base material and making the barrier layer with a predetermined thickness, the present invention allows an adhesive tape having the excellent properties of improving the contamination of a adherend with particles which are the residual adhesive on the adherend and providing the accuracy of thickness, in which fish-eyes and foreign substances are not included. This kind of the adhesive tape serves a useful function as a surface-protecting tape for various materials in the field of semiconductor, especially for example a semiconductor wafer in the step of grinding the back side of the wafer. Furthermore, a preferable base material having a breaking elongation of 10% or more can be obtained using a monomer having a ring structure as a reactive diluted monomer. The above and other objects, effects, features and advantages of the present invention will become more apparent from the following description of embodiments thereof taken in conjunction with the accompanying drawings. Fig. 1 is a schematic cross sectional view of a base material; and Fig. 2 is a schematic cross sectional view of an adhesive tape as embodiment of the present invention. Referring now to Fig. 1, we will describe a base material in detail. As shown in the figure, a layer of base material (hereinafter, referred as a base layer) 3 comprises a film layer 1 and a barrier layer 2 laminated on the film layer 1. The film layer 1 is provided as a film made of a radiation-cured resin such as one disclosed in Japanese Patent Application laying-open No. 9-253964 (1997). A composition of the resin mainly consists of an urethane acrylate oligomer and a reactive-diluted monomer, so that it can be cured by means of radiation such as ultraviolet radiation or electron radiation to form a film. The urethane (meth) acrylate oligomer to be used in the above composition may be a di-functional urethane (meth) acrylate with an ester-diol as its main skeleton, having a molecular weight preferably of 500 to 50,000, more preferably of 1,000 to 30,000. In this case, it may be of either polyester-polyol type or polyether-polyol type. Accordingly to the invention, the urethane (meth) acrylate oligomer may be used alone or in combination with one or more different types as a mixture thereof as necessary. The reactive-diluted monomer to be used in the above composition may be preferably a monofunctional diluted monomer, or more preferably a monomer having a ring structure. It may be selected from the group of: cycloaliphatic compounds including isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and adamantane (meth) acrylate; aromatic compounds including benzyl acrylate; and heterocyclic compounds including tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N-vinyl pyrolidone, and N-vinyl caprolactam. Alternatively, a multi-functional (meth) acrylate may be used optionally. For the above composition, a mixing ratio between the urethane (meth) acrylate oligomer and the reactive-diluted monomer is 95 to 5 : 5 to 95, preferably 50 to 70 : 50 to 30, based on a weight-percentage. In addition to the above components, the film layer 1 may further comprise one or more desired additives, for example a photo-initiator such as a benzoin compound, an acetophenone compound, an acylphosphinoxide compound, a titanocene compound, a thioxanthone compound, and a peroxide compound; a photo-sensitizer such as amine or quinone; and a colorant such as dye or pigment. One of preferable examples of the composition for forming the film layer 1 comprises: 100 parts by weight of a mixture of urethane (meth) acrylate oligomer and reactive-diluted monomer; and 0.1 to 10, or preferably 1 to 5 parts by weight of the photo-initiator. This kind of the film layer 1 can be prepared by forming a liquid resin of the above composition into a film by a conventional method. The conventional method comprises the steps of casting the resin by a fountain die or a comma coater and curing the casted resin by the application of a radiation such as UV or electron rays. A thickness of the resulting film layer 1 is preferably 50 to 1,995µm, or more preferably 100 to 490µm. It is preferable that an initial elastic coefficient of the film layer 1 is 100 to 100,000 kg/cm 2 , or preferably 500 to 50,000 kg/cm 2 , after the curing step. The barrier layer 2 may be enough to prevent the bleeding of unacceptable residual ingredients of low molecular weights from the film layer 1. The unacceptable residual ingredients are generated in the film layer 1 after the film-formation. The barrier layer 2 may be comprised of, for example polyethylene terephtalate (hereinafter, abbreviated as PET), polyethylene naphthalate (hereinafter, abbreviated as PEN), low-density polyethylene (hereinafter, abbreviated as LDPE), thermoplastic polyurethane, thermoplastic acrylate resin, polypropylene, polyethylene/(meth) acrylate copolymer, or the like. Furthermore, the composition for forming the barrier layer 2 may include one or more additional components such as a colorant and a stabilizer which are popularly accepted by those skilled in the art. The barrier layer 2 may be applied on the film layer 1 by welding or bonding a preformed film of the above composition to the film layer 1 by the conventional method such as a thermal welding. Alternatively, the barrier layer 2 may be formed on the film layer 1 using a commercially available film such as LDPE as it is. It is also possible to apply the barrier layer 2 on the film layer 1 by the process including the steps of preparing a solution of the above composition for producing a barrier layer and casting the solution on the film layer 1 by means of a die coater, a comma coater, a roll coater, a bar coater, or the like. The resulting barrier layer 2 has a thickness preferably of 0.1 to 40µm, or more preferably of 10 to 30µm, for the purpose of preventing both the generation of fish-eyes and the bleeding of unacceptable ingredients. In Fig. 1, as described above, the barrier layer 2 is only formed on one side of the film layer 1. According to the present invention, however, both sides of the film layer 1 may have the barrier layers 2 as necessary and one of them may perform another function related to, for example, an improvement in workability for the step of grinding the back side of a silicon wafer (hereinafter, this step is simply referred as the step of back-side grinding). The base layer 3 thus obtained has an initial elastic coefficient of 10 to 100,000 kg/cm 2 , preferably 100 to 50,000 kg/cm 2 ; a breaking elongation of 10% or more, or preferably 100% or more; and a 10% stress of 10 to 500 kg/cm 2 , or preferably 20 to 100 kg/cm 2 , which are based on Japanese Industrial Standard (hereinafter, abbreviated as JIS) K7127. If a monomer having a ring structure is used as the reactive-diluted monomer, a base layer 3 having a breaking elongation of 10% or more can be easily obtained. If the breaking elongation is less than 10%, on the other hand, there is the fear of generating cracks in the cured layer when an adhesive tape (which is provided as a base material coated with an adhesive agent) is adhered on a adherend by means of a conventional taping machine. An entire thickness of the base layer 3 is preferably 60 to 2,000µm, more preferably 100 to 500µm. Consequently, an adhesive tape of the present invention can be prepared using the base layer 3 obtained by the above procedure. Fig. 2 is a cross sectional view of the adhesive tape. In the figure, reference numerals 1 to 3 denote the same constituents as that of shown in Fig. 1, 4 denotes an adhesive layer, and 5 denotes an adhesive tape. The adhesive tape 5 is formed by further applying an adhesive layer 4 on a surface of the barrier layer 2 of the base layer 3. Constituents of the adhesive layer 4 may include those of the general adhesive tape such as a water-swelling type adhesive agent disclosed in Japanese Patent Application Publication No. 5-77284 (1993) and a radiation-hardening type adhesive agent disclosed in Japanese Patent Application Laying-open No. 62-153376 (1987). The adhesive layer 4 is applied on the barrier layer 2 by means of the conventional method using a comma coating, a die coating, or the like. Preferably, the adhesive layer 4 has a thickness of 5 to 100µm. In Fig. 2, by the way, the barrier layer 2 is only formed on one side of the film layer 1 and then the adhesive layer 4 is formed on a surface of the barrier layer 2. According to the present invention, however, both sides of the film layer 1 may have the barrier layers 2 as necessary and one side or both sides of the barrier layers 2 may have the adhesive layer(s) 4. Consequently, the adhesive tape 5 thus obtained has the advantages that: a desired thickness of the adhesive tape 5 is attained with great accuracy of thickness; a surface of the base layer 3 is free of fish-eyes and foreign substances; and the barrier layer 2 prevents the bleeding of unacceptable low-molecular-weight ingredients from the film layer 1 to the adhesive layer 4. In the semiconductor-manufacturing process, for example, the adhesive tape 5 can be used as a favorable surface-protecting tape in terms of residual particles on a semiconductor wafer when the tape is peeled off after the steps of sticking the tape on a surface of the wafer and grinding the opposite surface thereof. <Examples> The present invention will be more clearly understood with reference to the following examples. In Table 1, urethane (meth) acrylate oligomers, reactive diluted monomers, and barrier layers used in the examples are listed. <Example 1> A resin solution to be used for forming a film layer was prepared by mixing: 60 parts by weight of di-functional urethane acrylate with an average molecular weight of about 8000 (trade name: UX-3301, manufactured by Nippon Kayaku Co., Ltd.) as an urethane (meth) acrylate oligomer; 40 parts by weight of morpholine acrylate (trade name: ACMO, manufactured by Kojin Co., Ltd.) as a reactive-diluted monomer; 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photo-initiating agent; and 0.2 parts by weight of a phthalocyanine pigment. Then, the resin solution was applied on a surface of a PET film of 38µm in thickness (manufactured by Toray Co., Ltd.) as a casting-support film by means of a fountain die technique to make a film layer of 80µm in thickness. Immediately after the step of applying the resin solution, a LDPE GF-1 film of 30µm in thickness (manufactured by Tamapoly Co., Ltd.) was laminated as a barrier layer on the other side of the film layer. Subsequently, the laminate was exposed to UV radiation with a light quantity of 250 mJ/cm 2 from a high-pressure mercury lamp (160 W/cm power) at a distance of 10 cm to cause cross-link and curing of the resin, resulting in a base material having a support film. <Examples 2 to 4> In these examples, base materials with their respective support films were formed by the same procedure as that of Example 1 except that their mixing ratios of urethane (meth) acrylate oligomer and reactive-diluted monomer were different. That is, 30 parts by weight (Example 2), 50 parts by weight (Example 3), or 70 parts by weight (Example 4) of di-functional urethane acrylate with an average molecular weight of about 8000 (trade name: UX-3301, manufactured by Nippon Kayaku Co., Ltd.) as an urethane (meth) acrylate oligomer; and 70 parts by weight (Example 2), 50 parts by weight (Example 3), or 30 parts by weight (Example 4) of morpholine acrylate (trade name: ACMO, manufactured by Kojin Co., Ltd.) as a reactive-diluted monomer were formulated in the composition. <Examples 5 to 7> In these examples, base materials with their respective support films were formed by the same procedure as that of Example 1 except that their reactive-diluted monomers were different. That is, the reactive-diluted monomer was cyclohexylacrylate (Example 5), isobornylacrylate (Example 6), or benzylacrylate (Example 7). <Examples 8 to 11> In these examples, base materials with their respective support films were formed by the same procedure as that of Example 1 except of the follows. In each of these examples, that is, the barrier layer had its own type and thickness different from the other. In addition, a thickness of the film layer was changed as the thickness of the corresponding barrier layer was changed. In Example 8, the resin solution was applied on the PET film of a support film to make a film layer of 98µm in thickness. Then, a PET film of 12µm in thickness (manufactured by Toray Co., Ltd.) was used as a film for the barrier layer. In Example 9, the resin solution was applied on the PET film of support film to make a film layer of 98µm in thickness. Then, a PEN film of 12µm in thickness (manufactured by Teijin Co., Ltd.) was used as a film for the barrier layer. In Example 10, the resin solution was applied on the PET film of support film to make a film layer of 80µm in thickness. Then, a thermoplastic urethane elastomer film of 30µm in thickness (manufactured by Nisshinbouseki Co., Ltd.) was used as a film for the barrier layer. In Example 11, the resin solution was applied on the PET film of a support film to make a film layer of 110µm. Then a thermoplastic acryl resin (Trade name: Parachron W-197C, manufactured by Negami Kogyo Co., Ltd.) was used for the barrier layer. The thermoplastic acryl resin was applied on a surface of film layer side by means of a bar coater to make a film of 0.3µm in thickness after drying. <Comparative Example 1> A base material with a support film was formed by the same way as that of Example 1 except that the resin solution was applied to the support film to make a film layer of 110µm in thickness and the barrier layer was not formed. Adhesive tapes were manufactured using the base materials with the support film formed by Examples 1 to 11 and Comparative Example 1. For each of the base materials, an adhesive agent was applied on the barrier-layer-laminated side of the base film concurrently with peeling off the support film from the base material to make an adhesive coating of 20µm in thickness. In this case, the adhesive agent was a water-swelling acrylic adhesive agent (disclosed in Japanese Patent Application Laying-open 5-77284 (1993)) comprising (i) a copolymer of ethyl acrylate, vinyl acetate, and methacrylic acid and (ii) polyethylene glycol lauryl ether and crosslinking with zinc acetate under the presence of potassium hydroxide. The following evaluations were performed on the base materials and the adhesive tapes obtained by the above procedures. The evaluating items for each of the base materials were accuracy of thickness, initial elastic coefficient, breaking elongation, and 10% stress, while the evaluating items for each of the adhesive tapes were the number of fish-eyes, the property of back-side grinding when it is taped on the semiconductor wafer, and the number of particles remained on the wafer. We will explain these evaluating items and lists the obtained results in Table 2 below. (1) Accuracy of thickness of the base material 100 points were arbitrary sampled from an area of 100 m 2 of the base material and then a thickness of each point was measured. The accuracy of thickness [ R (µm)] was determined as a difference between the maximum and the minimum in the values of a series of measurements. (2) Initial elastic coefficient of the base material The measurement was performed at a testing speed of 200 mm per minute in conformity with JIS K7127. (3) Breaking elongation of the base material The measurement was performed at a testing speed of 200 mm per' minute in conformity with JIS K7127. (4) 10% stress of the base material The measurement was performed at a testing speed of 200 mm per minute in conformity with JIS K7127. (5) Number of fish-eyes in the adhesive tape A visual examination was performed on an area of 10 m 2 on a surface of each adhesive tape as a sample. A fish-eye with a height of 10µm or more was counted to obtain the number of fish-eyes in the adhesive tape. (6) Property of back-side grinding Using the respective adhesive tapes, 50 silicon wafers (8 inches in diameter) were subjected to the step of back-side grinding in which the back side of each wafer was ground by a grinder DFG 840 (manufactured by Disco Co., Ltd.) and then subjected to a visual examination. We examined that water penetration into a space between the wafer and the adhesive tape, peeling of the adhesive tape, and a fracture of the wafer. (7) Number of the particles Each of the adhesive tapes was adhered on a silicon wafer (4 inches in diameter) and then subjected to the step of back-side grinding as the same way as that of the above item (6). The number of particles (i.e., 0.27µm or more sized foreign substances) remained on a surface of the wafer was measured after peeling off the tape after 1 hour (23°C, 65% RH) and also after 7 days (40°C, drying). The measurement device used in this evaluation was a laser type surface-analyzing device LS-5000 manufactured by Hitachi Electronic Engineering Co., Ltd. Regarding the base materials obtained by casting the radiation-cured resin as the film layer, as is evident from the results listed in Table 2, each of them showed an excellent accuracy of thickness and a breaking elongation of 10% or more, which were extremely encouraging results. We also found that initial elongation coefficient and 10% stress were in their preferable ranges for our purpose. Furthermore, we could not observe any fish-eye and any foreign substances in each of the base materials. In the step of back-side grinding, furthermore, we could not find any abnormality in the silicon wafers being tested. Regarding the adhesive tapes of the present invention in which each of them uses the base material with the barrier layer (Examples 1 to 11), we obtained excellent results in a series of measurements on the number of particles. Regarding the adhesive tapes of Comparative Example 1, which did not have any barrier layer, the number of particles was increased when the back-side ground wafer was left for 7 days at a temperature of 40 °C under the drying condition. Therefore, it is apparent from the results that the silicon wafer becomes polluted with foreign substances or the like if the adhesive agent is directly applied on the film layer of the radiation-cured resin. In this case, it is assumed that unacceptable low-molecular-weight ingredients of some kind are dispersed into the adhesive layer and they pollute the wafer's surface. According to the present invention, however, the dispersion of the unacceptable ingredients can be prevented by providing the adhesive tape with the barrier layer as disclosed in Examples 1 to 11. Therefore, the undesired ingredients of the adhesive tape cannot pollute the wafer. As a consequence, the adhesive tape of the present invention, which is of a laminate type, is far superior to the conventional one as a surface-protective tape for a silicon wafer when the silicon wafer is subjected to the process of manufacturing a semiconductor, especially in the step of back-side grinding.

Claims: An adhesive tape (5) comprising: a base material (3) having a film layer (1) which is a radiation cured mixture of urethane (meth) acrylate oligomer and reactive-diluted monomer, and a barrier layer (2) on at least one surface of the film layer; and an adhesive layer (4) on the surface of the barrier layer. An adhesive tape according to claim 1, wherein the reactive-diluted monomer has a cyclic structure. An adhesive tape according to claim 2, wherein the reactive-diluted monomer is selected from cycloaliphatic compounds, aromatic compounds and heterocyclic compounds. An adhesive tape according to any one of claims I to 3, wherein the barrier layer (2) has a thickness of 0.1 to 40 µm.

Inventors: EBE KAZUYOSHI, KONDOH TAKESHI, NAGAMOTO KOUICHI, TAGUCHI KATSUHISA, TAKAHASHI KAZUHIRO, EBE, KAZUYOSHI, KONDOH, TAKESHI, NAGAMOTO, KOUICHI, TAGUCHI, KATSUHISA, TAKAHASHI, KAZUHIRO
Applicants: LINTEC CORP, LINTEC CORPORATION
Application year: 1998
Main classification: C09J7
IPC codes: B32B27, C09J7, H01L21, C09J133, C08F290