JP4976532B2 - Film for semiconductor devices - Google Patents

Abstract

Provided is an adhesive film with a dicing sheet (1), wherein the adhesive film (12) is laminated on top of a dicing film (11), which has excellent reliability and is readily capable of tip protrusion (tongue protrusion) of a cover film (2) while maintaining a function for suppressing the formation of transfer marks when a film (10) for a semiconductor device, wherein the adhesive film with the dicing sheet is laminated at prescribed intervals on the cover film, is wound into a roll. The film for a semiconductor device of the present invention is a film for a semiconductor device wherein the adhesive film with a dicing sheet, which is the adhesive film laminated on top of a dicing film, is laminated to the cover film at prescribed intervals, and said film for a semiconductor device has an Ea/Eb ratio between the tensile storage modulus (Ea) for the dicing film at 23°C and the tensile storage modulus (Eb) for the cover film at 23°C of 0.001-100.

Description

  The present invention relates to a film for a semiconductor device and a semiconductor device manufactured using the film for a semiconductor device.

  Conventionally, silver paste is used for fixing a semiconductor chip to a lead frame or an electrode member in a manufacturing process of a semiconductor device. The fixing process is performed by applying a paste adhesive on a die pad or the like of the lead frame, mounting a semiconductor chip on the lead adhesive, and curing the paste adhesive layer.

  However, paste adhesives have large variations in coating amount, coating shape, etc. due to their viscosity behavior and deterioration. As a result, the thickness of the paste-like adhesive formed is not uniform, and the reliability of the fixing strength related to the semiconductor chip is poor. That is, when the application amount of the paste adhesive is insufficient, the bonding strength between the semiconductor chip and the electrode member is lowered, and the semiconductor chip is peeled off in the subsequent wire bonding process. On the other hand, when the application amount of the paste adhesive is too large, the paste adhesive is cast onto the semiconductor chip, resulting in poor characteristics, and the yield and reliability are lowered. Such a problem in the adhering process becomes particularly remarkable as the semiconductor chip becomes larger. Therefore, it is necessary to frequently control the amount of paste adhesive applied, which hinders workability and productivity.

  In this paste adhesive application step, there is a method in which the paste adhesive is separately applied to a lead frame or a formed chip. However, in this method, it is difficult to make the paste adhesive layer uniform, and a special apparatus and a long time are required for applying the paste adhesive. For this reason, a dicing film and an adhesive film with a dicing sheet for adhering and holding a semiconductor wafer in a dicing process and also providing an adhesive layer for chip fixation necessary for the mounting process have been proposed (for example, see Patent Document 1). ).

  This adhesive film with a dicing sheet is formed by providing an adhesive layer on a supporting substrate so that the adhesive layer can be peeled off, and is formed by dicing a semiconductor wafer while being held by the adhesive layer and then stretching the supporting substrate. The chip is peeled off together with the adhesive layer, and the chips are individually collected and fixed to an adherend such as a lead frame through the adhesive layer.

  Conventionally, an adhesive film with a dicing sheet has been manufactured by individually bonding a dicing film and an adhesive film, due to restrictions in the manufacturing process. For this reason, from the viewpoint of preventing the occurrence of slack, winding deviation, positional deviation, voids (bubbles), etc. in each film production process, the production is performed while applying tensile tension to each film during conveyance by a roll. .

  This type of adhesive film with a dicing sheet may be cured when placed in a high-temperature and high-humidity environment or stored for a long time under a load. As a result, the fluidity of the adhesive layer, the holding power against the semiconductor wafer, and the peelability after dicing are reduced. For this reason, the adhesive film with a dicing sheet is often transported while being stored in a frozen state at -30 to -10 ° C or a refrigerated state at -5 to 10 ° C, thereby enabling long-term storage of film characteristics. ing.

  The adhesive film with a dicing sheet described above is processed in advance into the shape of a semiconductor wafer to be attached (for example, a circular shape) in consideration of workability such as attachment to a semiconductor wafer and attachment to a ring frame during dicing. There are those that have been pre-cut.

  Such an adhesive film with a dicing sheet is obtained by laminating an adhesive film punched in a circular shape on a dicing film in which an adhesive layer is laminated on a substrate, and then dicing the dicing film into a circular shape corresponding to the ring frame. Manufactured by punching. Thereby, when dicing a semiconductor wafer, a ring frame can be affixed to the outer peripheral part of a dicing film, and an adhesive film with a dicing sheet can be fixed here now.

  The adhesive film with a dicing sheet that has been pre-cut is attached to a long cover film at a predetermined interval, and then wound into a roll, and is transported and stored as a film film for a semiconductor device.

JP-A-60-57642

  However, in the case of the film for a semiconductor device described above, the thickness of the portion where the adhesive film with a dicing sheet is laminated is thicker than the thickness of the portion where it is not laminated. Therefore, especially when the number of windings is increased or the tension at the time of winding is increased, the edge of another adhesive film with a dicing sheet is pressed against the adhesive film with another dicing sheet, and the trace is transferred. The smoothness of the adhesive film may be impaired. Such transfer marks are particularly prominent when the adhesive film is formed of a relatively soft resin, when the adhesive film is thick, and when the number of windings of the film for a semiconductor device is large. When an adhesive film having such transfer marks and having a smoothness defect is attached to a semiconductor wafer, voids (bubbles) are generated between the semiconductor wafer and the adhesive film. Such voids cause problems during the processing of semiconductor wafers, and may reduce the yield of manufactured semiconductor devices.

  Therefore, in order to suppress the generation of the transfer mark, a method of reducing the winding pressure of the film for a semiconductor device can be considered. However, in this method, winding deviation occurs, and there is a possibility that troubles may occur during actual use, for example, it becomes difficult to set the tape mounter.

Moreover, in order to suppress generation | occurrence | production of the said transfer trace, it is possible to provide a buffer base material in the back surface side of an adhesive sheet. However, this kind of adhesive film with a dicing sheet, when stored for a long time under high temperature and high humidity or under load, the dicing film and the adhesive film are cured, the holding power to the semiconductor wafer is reduced, or peeling after dicing Properties, fluidity during molding, and the like are reduced. Therefore, the adhesive film with a dicing sheet is often transported at a low temperature in a frozen state or a refrigerated state. However, residual stress remains between the adhesive film and the buffer base material, so that both of them at the interface between the adhesive film and the buffer base material after transportation in the low temperature state and storage for a long time described above. There is a problem of causing peeling. Here, each temperature range of freezing and refrigeration is a range of about -30 ° C to -10 ° C for freezing, and -5 ° C to 10 ° C for refrigeration.

  Also, if the temperature change is large as in the above environment, stress concentration occurs from the cover film side and the base material side constituting the dicing film, and the force that can not be absorbed or dispersed damages the adhesive film, A transfer mark is generated on the adhesive film, or the adhesive film is cracked or chipped at the time of wafer mounting. Also, if the cover film has a low modulus of elasticity, a defect that prevents the film from leading out (veloping) when peeling the cover film during wafer mounting occurs, the machine stops due to a transport error, or the cover film is attached. The process proceeds to wafer bonding, and the wafer is laminated on the cover film. And since it is conveyed in the state which is not closely_contact | adhering, a wafer may be broken.

  SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a film for a semiconductor device in which an adhesive film with a dicing sheet in which an adhesive film is laminated on a dicing film is laminated on a cover film at a predetermined interval. It is an object to provide an adhesive film with a dicing sheet that is capable of easily leading out (veloping out) a cover film while maintaining the function of suppressing transfer marks when the film is rolled up.

  The inventors of the present application have studied a film for a semiconductor device in order to solve the conventional problems. As a result, by controlling the tensile storage modulus of the dicing film constituting the film for semiconductor devices and the tensile storage modulus of the cover film, it is possible to suppress the generation of transfer marks on the die bond film, and the tip of the cover film. The present invention was completed by finding out that the feeding (bello feeding) can be easily performed.

  That is, the film for a semiconductor device according to the present invention is a film for a semiconductor device in which an adhesive film with a dicing sheet obtained by laminating an adhesive film on a dicing film is laminated on a cover film at a predetermined interval. The ratio Ea / Eb of the tensile storage elastic modulus Ea of the dicing film and the tensile storage elastic modulus Eb of the cover film at 23 ° C. is in the range of 0.001 to 100.

  The larger the value of Ea / Eb, the harder the dicing film and the softer the cover film. On the other hand, the smaller the value of Ea / Eb, the softer the dicing film and the harder the cover film. According to the said structure, since said Ea / Eb is 0.001 or more, the hardness (tensile storage elastic modulus Ea) of a dicing film becomes fixed or more. Therefore, it can suppress that a transfer mark generate | occur | produces in the adhesive film which comprises an adhesive film with a dicing sheet. Further, since the Ea / Eb is 0.001 or more and the hardness (tensile storage elastic modulus Ea) of the dicing film is a certain value or more, the dicing sheet having the dicing film is bonded to the semiconductor wafer. The attached adhesive film and the cover film can be suitably peeled off.

Further, since the Ea / Eb is 100 or less, the hardness of the cover film (tensile storage elastic modulus Eb) is not less than a certain value, while the hardness of the dicing film (tensile storage elastic modulus Ea) is not more than a certain value. Become. Therefore, it is possible to prevent the cover film from being broken when the adhesive film is bonded to the cover film, and to prevent the adhesive film surface from being damaged or air bubbles from being mixed between the films. . As a result, it is possible to suppress the generation of voids between the adhesive film and the semiconductor wafer when the cover film is lifted or the semiconductor wafer is mounted.
Thus, according to the said structure, when winding up in roll shape, it can suppress that a transfer trace generate | occur | produces on an adhesive film. Moreover, it is possible to suppress the occurrence of voids (bubbles) between the adhesive film and the semiconductor wafer when the cover film is lifted or the semiconductor wafer is mounted.

  Said structure WHEREIN: It is preferable that the said adhesive film has the glass transition temperature in the range of 0-100 degreeC, and the tensile storage elastic modulus in 23 degreeC before hardening is the range of 50 MPa-5000 MPa. By making the glass transition temperature of the said adhesive film 0 degreeC or more, it can suppress that the tackiness of the adhesive film in a B stage state becomes large, and can maintain favorable handleability. Further, when dicing, it is possible to prevent a part of the adhesive film from melting and the pressure-sensitive adhesive from adhering to the semiconductor chip. As a result, a good pick-up property of the semiconductor chip can be maintained. On the other hand, the fluidity | liquidity fall of an adhesive film can be prevented by making glass transition temperature into 100 degrees C or less. Moreover, the favorable adhesiveness with a semiconductor wafer can also be maintained. In addition, when an adhesive film is a thermosetting type, the glass transition temperature of an adhesive film means the thing before thermosetting. In addition, by setting the tensile storage modulus at 23 ° C. before curing of the adhesive film to 50 MPa or more, a part of the pressure-sensitive adhesive layer is prevented from melting and adhering to the semiconductor chip during dicing. be able to. On the other hand, by setting the tensile storage modulus to 5000 MPa or less, it is possible to maintain good adhesion to a semiconductor wafer or substrate.

  The said structure WHEREIN: It is preferable that the thickness of the said cover film is 10-100 micrometers.

  The said structure WHEREIN: It is preferable that the thickness of the said dicing film is 25-180 micrometers.

  The said structure WHEREIN: It is preferable that the tensile storage elastic modulus Ea of a dicing film in 23 degreeC is 1-500 Mpa.

  The said structure WHEREIN: It is preferable that the tensile storage elastic modulus Eb of a cover film in 23 degreeC is 1-5000 Mpa.

  A semiconductor device according to the present invention is manufactured using the film for a semiconductor device described above.

(A) is a top view which shows the outline of the film for semiconductor devices which concerns on this embodiment, (b) is the fragmentary sectional view. It is a fragmentary sectional view in the state where the film for semiconductor devices shown in Drawing 1 (a) and Drawing 1 (b) was rolled up. It is the schematic for demonstrating the manufacturing process of the film for semiconductor devices.

The film for a semiconductor device according to the present embodiment will be described below.
Fig.1 (a) is a top view which shows the outline of the film for semiconductor devices which concerns on this embodiment, FIG.1 (b) is the fragmentary sectional view. The film 10 for a semiconductor device has a configuration in which an adhesive film 1 with a dicing sheet is laminated on a cover film 2 at a predetermined interval. The adhesive film 1 with a dicing sheet has a structure in which an adhesive film 12 is laminated on a dicing film 11, and the dicing film 11 has a structure in which an adhesive layer 14 is laminated on a base material 13.

  FIG. 2 is a partial cross-sectional view of the semiconductor device film shown in FIGS. 1A and 1B wound in a roll shape. As shown in FIG. 2, in the film 10 for a semiconductor device wound in a roll shape, there is a step 19 between a portion where the adhesive film 1 with a dicing sheet is laminated and a portion 18 where the adhesive film 1 is not laminated. Moreover, the several adhesive film 1 with a dicing sheet on the cover film 2 is laminated | stacked, mutually shifting | deviating to a horizontal direction. Therefore, the edge of the other adhesive film 1 with a dicing sheet is pressed against one adhesive film 1 with a dicing sheet.

  In the film 10 for semiconductor devices, the ratio Ea / Eb between the tensile storage elastic modulus Ea of the dicing film 11 at 23 ° C. and the tensile storage elastic modulus Eb of the cover film 2 at 23 ° C. is in the range of 0.001 to 100. . The Ea / Eb is preferably 0.01 to 50, and more preferably 0.1 to 5. As the value of Ea / Eb is larger, the dicing film 11 is relatively harder and the cover film 2 is softer. On the other hand, the smaller the value of Ea / Eb, the softer the dicing film 11 and the harder the cover film 2. According to the film 10 for a semiconductor device, since the Ea / Eb is 0.001 or more, the hardness (tensile storage elastic modulus Ea) of the dicing film 11 becomes a certain value or more. Therefore, it can suppress that a transfer mark generate | occur | produces in the adhesive film 12 which comprises the adhesive film 1 with a dicing sheet. Moreover, according to the film 10 for semiconductor devices, since the Ea / Eb is 0.001 or more and the hardness (tensile storage elastic modulus Ea) of the dicing film 11 is more than a certain value, it is bonded to a semiconductor wafer. In this case, the adhesive film with a dicing sheet 1 having the dicing film 11 and the cover film 2 can be suitably peeled off (develop).

Further, since Ea / Eb is 100 or less, the hardness of the cover film 2 (tensile storage elastic modulus Eb) is not less than a certain value, while the hardness of the dicing film 11 (tensile storage elastic modulus Ea) is constant. It becomes as follows. Therefore, it is possible to prevent the cover film 2 from being folded when the adhesive film 12 is bonded to the cover film 2, and to prevent the surface of the adhesive film 12 from being damaged or air bubbles from being mixed between the films. can do. As a result, it is possible to suppress the generation of voids between the adhesive layer and the semiconductor wafer when the cover film 2 is lifted or the semiconductor wafer is mounted.
Thus, according to the film 10 for semiconductor devices, it is possible to prevent the transfer mark from being generated on the adhesive film 12 when the film is wound into a roll. Moreover, it can suppress that a void (bubble) generate | occur | produces between the adhesive film 12 and a semiconductor wafer at the time of the film floating of the cover film 2, or the mounting of a semiconductor wafer.

The peel force F ₁ between the adhesive film 12 and the cover film 2 is preferably smaller than the peel force F ₂ between the adhesive film 12 and the dicing film 11. The film 10 for semiconductor devices is applied with tensile tension to the dicing film 11, the adhesive film 12, and the cover film 2 from the viewpoint of preventing the occurrence of loosening, winding deviation, positional deviation, voids (bubbles), etc. in the manufacturing process. Laminated and manufactured. Therefore, each film has a tensile residual strain. This tensile residual strain causes, for example, shrinkage of each film when it is transported in a frozen state of −30 to −10 ° C. or transported in a low temperature state of −5 to 10 ° C. or stored for a long time. For example, the dicing film has the largest degree of shrinkage and the cover film has the smallest degree of shrinkage. Here, in the film for a semiconductor device according to the present embodiment, the peeling forces F ₁ and F ₂ are in a relationship of F ₁ <F ₂ , whereby the interface between the films due to the difference in shrinkage between the films. Peeling and film floating phenomenon of the cover film 2 can be prevented. Furthermore, it is possible to prevent a part or all of the adhesive film 12 from being transferred to the cover film 2.

The peel force F ₁ between the adhesive film 12 and the cover film 2 is preferably in the range of 0.025 to 0.075 N / 100 mm, more preferably in the range of 0.03 to 0.06 N / 100 mm, and 0.035 to A range of 0.05 N / 100 mm is particularly preferable. When the peeling force _{F 1} is less than 0.025 N / 100 mm, for example -30 to-10 ° C. refrigeration, or was stored a long time or transported at low temperature state of -5～10 ° C., the adhesive film 12 and the cover The films 2 may shrink at different shrinkage rates, which may cause a film floating phenomenon of the cover film 2. In addition, wrinkles, winding deviations, and foreign matters may be generated during the transport of the semiconductor device film 10 or the like. Furthermore, a void (bubble) may be generated between the adhesive film 12 and the semiconductor wafer when the semiconductor wafer is mounted. Meanwhile, the peel force _{F 1} is larger than 0.075N / 100mm, since adhesion of the adhesive film 12 and the cover film 2 is too strong, when the peeling of the cover film 2 and its retracted, constituting the adhesive film 12 The adhesive (details will be described later) may be transferred to a part or the entire surface. Incidentally, the value of the peeling force F _1, when the adhesive film 12 is thermally curable is meant a peel force between the adhesive film 12 and the cover film 2 before thermal curing.

Further, the peeling force _{F 2} between the adhesive film 12 and the dicing film 11 is preferably in the range of 0.08~10N / 100mm, and more preferably in the range of 0.1~6N / 100mm, 0.15~0. A range of 4 N / 100 mm is particularly preferable. When the peeling force F2 is 0.08 N / 100 mm or more, for example, in the case of freezing at −30 to −10 ° C. or transporting in a low temperature state of −5 to 10 ° C. or storing for a long time, the dicing film 11 and the adhesive film 12 can be prevented from shrinking at different shrinkage rates, thereby preventing interfacial peeling between the dicing film 11 and the adhesive film 12. Further, it is possible to prevent the generation of wrinkles, winding misalignment, mixing of foreign matters, and voids during the transport of the semiconductor device film 10 and the like. Furthermore, chip jumping and chipping can be prevented when dicing the semiconductor wafer. On the other hand, when the peel force F ₂ is less than 10 N / 100 mm, when the pickup of the semiconductor chip, peeling property be suitable between the adhesive film 12 and the adhesive layer 14, good pickup of the semiconductor chip can do. Moreover, it is possible to prevent the adhesive from adhering to the adhesive (details will be described later) constituting the adhesive layer 14 on the semiconductor chip with adhesive. The numerical range of the peeling force F ₂ is in pressure-sensitive adhesive layer in the dicing film 11 is ultraviolet curable and also encompasses a case where the predetermined curing degree by beforehand ultraviolet irradiation. Moreover, hardening of the adhesive layer by ultraviolet irradiation may be before bonding with the adhesive film 12, and may be after bonding.

The values of the peeling forces F ₁ and F ₂ are measured values in a T-type peeling test (JIS K6854-3) performed under conditions of a temperature of 23 ± 2 ° C., a peeling speed of 300 mm / min, and a distance between chucks of 100 mm. As a tensile tester, a trade name “Autograph AGS-H” (manufactured by Shimadzu Corporation) was used.

  The base material 13 in the dicing film 11 serves as a strength matrix for the semiconductor device film 10 as well as the dicing film 11. Examples of the base material 13 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, and the like. Polyolefin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene -Hexene copolymers, polyesters such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyetherimide, polyamide, wholly aromatic polyamide, polyphenyl Rufuido, aramid (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, metal (foil), paper, and the like. In the case where the pressure-sensitive adhesive layer 14 is of an ultraviolet curable type, the substrate 13 is preferably one having ultraviolet transparency among those exemplified above.

  Moreover, as a material of the base material 13, polymers, such as the crosslinked body of the said resin, are mentioned. The plastic film may be used unstretched or may be uniaxially or biaxially stretched as necessary. According to the resin sheet imparted with heat shrinkability by stretching or the like, the adhesive area between the pressure-sensitive adhesive layer 14 and the adhesive film 12 is reduced by thermally shrinking the base material 13 after dicing, and the semiconductor chip can be recovered. Simplification can be achieved.

  The surface of the substrate 13 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion and retention with adjacent layers. Alternatively, a physical treatment or a coating treatment with a primer (for example, an adhesive substance described later) can be performed.

  As the base material 13, the same kind or different kinds can be appropriately selected and used, and a blend of several kinds can be used as necessary. Further, in order to impart antistatic ability to the base material 13, a conductive material vapor deposition layer having a thickness of about 30 to 500 mm made of metal, alloy, oxides thereof, or the like may be provided on the base material 13. it can. The substrate 13 may be a single layer or a multilayer of two or more types.

  The thickness of the base material 13 is 10 to 170 μm in order to ensure the film transportability and prevent the base material 13 from being torn, torn or plastically deformed even when the supporting base material is expanded in the bonding process. More preferably, it is 50-150 micrometers, More preferably, it is 100-130 micrometers.

  It does not restrict | limit especially as an adhesive used for formation of the adhesive layer 14, For example, common pressure sensitive adhesives, such as an acrylic adhesive and a rubber adhesive, can be used. The pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive based on an acrylic polymer from the standpoint of cleanability with an organic solvent such as ultrapure water or alcohol for electronic components that are difficult to contaminate semiconductor wafers and glass. Is preferred.

  Examples of the acrylic polymer include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester , Octadecyl esters, eicosyl esters, etc., alkyl groups having 1 to 30 carbon atoms, especially 4 to 18 carbon linear or branched alkyl esters, etc.) and Meth) acrylic acid cycloalkyl esters (e.g., cyclopentyl ester, acrylic polymers such as one or more was used as a monomer component of the cyclohexyl ester etc.). In addition, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and (meth) of the present invention has the same meaning.

  The acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. You may go out. Examples of such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate Hydroxyl group-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; Styrene Contains sulfonic acid groups such as phonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid Monomers; Phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; acrylamide, acrylonitrile and the like. One or more of these copolymerizable monomer components can be used. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total monomer components.

  Furthermore, since the acrylic polymer is crosslinked, a polyfunctional monomer or the like can be included as a monomer component for copolymerization, if necessary. Examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 30% by weight or less of the total monomer components from the viewpoint of adhesive properties and the like.

  The acrylic polymer can be obtained by subjecting a single monomer or a mixture of two or more monomers to polymerization. The polymerization can be performed by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. From the viewpoint of preventing contamination of a clean adherend, the content of the low molecular weight substance is preferably small. From this point, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably about 400,000 to 1,500,000.

  In addition, an external cross-linking agent can be appropriately employed for the pressure-sensitive adhesive in order to increase the number average molecular weight of an acrylic polymer as a base polymer. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them. When using an external cross-linking agent, the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive. Generally, it is preferable to add about 5 parts by weight or less, and further 0.1 to 5 parts by weight with respect to 100 parts by weight of the base polymer. Furthermore, you may use additives, such as conventionally well-known various tackifier and anti-aging agent, other than the said component as needed to an adhesive.

  The pressure-sensitive adhesive layer 14 can be formed of an ultraviolet curable pressure-sensitive adhesive. The UV curable pressure-sensitive adhesive can easily reduce its adhesive strength by increasing the degree of crosslinking by irradiation with ultraviolet rays, and by irradiating only the portion corresponding to the semiconductor wafer attachment portion of the pressure-sensitive adhesive layer 14 with UV irradiation. A difference in adhesive strength with other portions can be provided.

The tensile storage elastic modulus Ea of the dicing film 11 at 23 ° C. is preferably in the range of 1 to 500 MPa, and more preferably in the range of 5 to 200 MPa. When the pressure-sensitive adhesive layer 14 is formed of an ultraviolet curable pressure-sensitive adhesive, the tensile storage elastic modulus Ea of the dicing film 11 at 23 ° C. after the pressure-sensitive adhesive layer 14 is ultraviolet-cured is in the range of 1 to 500 MPa. Preferably, the range of 5 to 200 MPa is more preferable. By setting the tensile storage elastic modulus Ea to 1 MPa or more, good pickup properties can be maintained. On the other hand, when the tensile storage elastic modulus Ea is set to 500 MPa or less, occurrence of chip jumping can be prevented. Further, since the dicing film 11 can be expanded, adjacent chips can be brought into contact with each other to prevent the occurrence of cracks and sticking, thereby realizing good pickup properties. In addition, it is preferable that the said ultraviolet irradiation is performed by the ultraviolet irradiation integrated light quantity of 30-1000mJ / cm < ² >, for example. By making the UV irradiation cumulative light quantity 30 mJ / cm ² or more, the pressure-sensitive adhesive layer 14 can be cured without deficiency, and excessive adhesion with the adhesive film 12 can be prevented. As a result, a good pick-up property can be exhibited when picking up a semiconductor chip. Further, it is possible to prevent the adhesive of the adhesive layer 14 from adhering to the adhesive film 12 after picking up (so-called adhesive residue). On the other hand, by reducing the cumulative amount of UV irradiation to 1000 mJ / cm ² or less, the adhesive layer 14 is prevented from being extremely reduced in adhesive force, thereby being peeled from the adhesive film 12 and mounted. Prevents the semiconductor wafer from falling off. Further, it is possible to prevent the chip jump of the formed semiconductor chip from occurring during the dicing of the semiconductor wafer.

The value of the tensile storage elastic modulus Ea of the dicing film 11 is based on the following measuring method. That is, a solution of the pressure-sensitive adhesive composition is applied onto a release liner that has been subjected to a release treatment and dried, and a substrate is bonded to the surface of the pressure-sensitive adhesive layer to form a dicing film. Using this dicing film, the tensile storage elastic modulus at 23 ° C. of the dicing film 11 is measured using a viscoelasticity measuring device (Rheometrics: model: RSA-II). More specifically, a measurement sample having a length of 30.0 mm × a width of 5.0 mm and a cross-sectional area of 0.125 to 0.9 mm ² is set on a film tension measuring jig, and is in a temperature range of −30 ° C. to 100 ° C. The measurement is performed under the conditions of a frequency of 10.0 Hz, a strain of 0.025%, and a heating rate of 10 ° C./min.

  Here, the adhesive film 12 has a configuration that is formed only on the affixed portion according to the shape of the semiconductor wafer in plan view. Therefore, by curing the ultraviolet curable pressure-sensitive adhesive layer 14 in accordance with the shape of the adhesive film 12, the adhesive strength of the portion corresponding to the semiconductor wafer attachment portion can be easily reduced. Since the adhesive film 12 is affixed to the portion where the adhesive strength is reduced, the interface between the portion of the pressure-sensitive adhesive layer 14 and the adhesive film 12 has a property of being easily peeled off during pickup. On the other hand, the part which is not irradiated with ultraviolet rays has sufficient adhesive force.

  As described above, the portion where the pressure-sensitive adhesive layer 14 is formed of an uncured ultraviolet curable pressure-sensitive adhesive adheres to the adhesive film 12 and can secure a holding force when dicing. As described above, the ultraviolet curable pressure-sensitive adhesive can support the adhesive film 12 for fixing a chip-shaped semiconductor wafer (semiconductor chip or the like) to an adherend such as a substrate with a good balance of adhesion and peeling. When the adhesive film 12 is laminated only on the portion where the semiconductor wafer is attached, the wafer ring is fixed in a region where the adhesive film 12 is not laminated.

  As the ultraviolet curable pressure-sensitive adhesive, those having an ultraviolet curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. Examples of the ultraviolet curable pressure-sensitive adhesive include an additive-type ultraviolet curable pressure-sensitive adhesive in which an ultraviolet curable monomer component or an oligomer component is blended with a general pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive or the rubber-based pressure-sensitive adhesive. An agent can be illustrated.

  Examples of the UV curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Examples include stall tetra (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. Examples of the ultraviolet curable oligomer component include urethane, polyether, polyester, polycarbonate, and polybutadiene oligomers, and those having a molecular weight in the range of about 100 to 30000 are suitable. The blending amount of the ultraviolet curable monomer component and oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer. Generally, the amount is, for example, about 5 to 500 parts by weight, preferably about 40 to 150 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.

  In addition to the additive-type UV-curable pressure-sensitive adhesive described above, the UV-curable pressure-sensitive adhesive has a carbon-carbon double bond in the polymer side chain, main chain, or main chain terminal as a base polymer. Intrinsic ultraviolet curable pressure sensitive adhesives using Intrinsic UV curable adhesives do not need to contain oligomer components, which are low molecular weight components, or do not contain many, so they are stable without the oligomer components moving through the adhesive over time. It is preferable because an adhesive layer having a layered structure can be formed.

  As the base polymer having a carbon-carbon double bond, those having a carbon-carbon double bond and having adhesiveness can be used without particular limitation. As such a base polymer, those having an acrylic polymer as a basic skeleton are preferable. Examples of the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.

  The method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted. However, the carbon-carbon double bond can be easily introduced into the polymer side chain for easy molecular design. . For example, after a monomer having a functional group is previously copolymerized with an acrylic polymer, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into an ultraviolet curable carbon-carbon double bond. A method of performing condensation or addition reaction while maintaining the above.

  Examples of combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups, and the like. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction. Moreover, the functional group may be on either side of the acrylic polymer and the compound as long as the acrylic polymer having the carbon-carbon double bond is generated by a combination of these functional groups. In the preferable combination, it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. Further, as the acrylic polymer, those obtained by copolymerizing the above-exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like are used.

  As the intrinsic ultraviolet curable pressure-sensitive adhesive, the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the ultraviolet curable monomer does not deteriorate the characteristics. Components and oligomer components can also be blended. The UV-curable oligomer component or the like is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight with respect to 100 parts by weight of the base polymer.

  The ultraviolet curable pressure-sensitive adhesive contains a photopolymerization initiator when cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethylacetophenone, 2-methyl-2-hydroxypropio Α-ketol compounds such as phenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- ( Acetophenone compounds such as methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyldimethyl ketal; 2-naphthalenesulfonyl Black Aromatic sulfonyl chloride compounds such as 1; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3,3′-dimethyl Benzophenone compounds such as -4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 Thioxanthone compounds such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; acyl phosphinoxide; acyl phosphonate. The compounding quantity of a photoinitiator is about 0.05-20 weight part with respect to 100 weight part of base polymers, such as an acryl-type polymer which comprises an adhesive.

  The ultraviolet curable pressure-sensitive adhesive layer 14 may contain a compound that is colored by ultraviolet irradiation, if necessary. By including a compound to be colored in the pressure-sensitive adhesive layer 14 by irradiation with ultraviolet rays, only the portion irradiated with ultraviolet rays can be colored. Thereby, it can be immediately determined by visual observation whether the adhesive layer 14 is irradiated with ultraviolet rays, the semiconductor wafer attachment portion can be easily recognized, and the semiconductor wafer can be easily attached. In addition, when detecting a semiconductor chip by an optical sensor or the like, the detection accuracy is increased, and no malfunction occurs when the semiconductor chip is picked up.

  A compound that is colored by ultraviolet irradiation is a compound that is colorless or light-colored before ultraviolet irradiation, but becomes colored by ultraviolet irradiation. Preferable specific examples of such compounds include leuco dyes. As the leuco dye, conventional triphenylmethane, fluoran, phenothiazine, auramine, and spiropyran dyes are preferably used. Specifically, 3- [N- (p-tolylamino)]-7-anilinofluorane, 3- [N- (p-tolyl) -N-methylamino] -7-anilinofluorane, 3- [ N- (p-tolyl) -N-ethylamino] -7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, crystal violet lactone, 4,4 ', 4 "-trisdimethyl Examples include aminotriphenylmethanol, 4,4 ′, 4 ″ -trisdimethylaminotriphenylmethane, and the like.

  Developers preferably used together with these leuco dyes include conventionally used initial polymers of phenol formalin resins, aromatic carboxylic acid derivatives, electron acceptors such as activated clay, and further change the color tone. In some cases, various known color formers can be used in combination.

  Such a compound colored by ultraviolet irradiation may be once dissolved in an organic solvent or the like and then contained in the ultraviolet curable pressure sensitive adhesive, or may be finely powdered and contained in the pressure sensitive adhesive. The use ratio of this compound is 10% by weight or less in the pressure-sensitive adhesive layer 14, preferably 0.01 to 10% by weight, more preferably 0.5 to 5% by weight. If the ratio of the compound exceeds 10% by weight, the ultraviolet ray irradiated to the pressure-sensitive adhesive layer 14 is excessively absorbed by the compound, so that the portion of the pressure-sensitive adhesive layer 14 corresponding to the semiconductor wafer attachment portion is not cured. It may be sufficient and the adhesive strength may not be sufficiently reduced. On the other hand, in order to sufficiently color, it is preferable that the ratio of the compound is 0.01% by weight or more.

  Further, when the pressure-sensitive adhesive layer 14 is formed of an ultraviolet curable pressure-sensitive adhesive, all or a part of the base material 13 other than the part corresponding to the semiconductor wafer pasting part is shielded from light. It is possible to form the portion with reduced adhesive force by forming the ultraviolet curable pressure-sensitive adhesive layer 14 and then irradiating it with ultraviolet rays to cure the portion corresponding to the semiconductor wafer attachment portion. As a light shielding material, what can become a photomask on a support film can be prepared by printing, vapor deposition, or the like. According to this manufacturing method, the film 10 for a semiconductor device of the present invention can be efficiently manufactured.

  In the case where curing inhibition occurs due to oxygen during ultraviolet irradiation, it is desirable to block oxygen (air) from the surface of the ultraviolet curable pressure-sensitive adhesive layer 14 by some method. For example, a method of covering the surface of the pressure-sensitive adhesive layer 14 with a separator, a method of irradiating ultraviolet rays in a nitrogen gas atmosphere, and the like can be mentioned.

  The thickness of the pressure-sensitive adhesive layer 14 is not particularly limited, but is preferably about 1 to 50 μm from the viewpoint of preventing chipping of the chip cut surface and compatibility of fixing and holding the adhesive film. Preferably it is 2-30 micrometers, Furthermore, 5-25 micrometers is preferable.

  Further, the total thickness of the base material 13 and the pressure-sensitive adhesive layer 14, that is, the thickness of the dicing film 11 is from the viewpoint of transportability, chip chipping surface chipping prevention, fixing and holding of the adhesive film, and pick-up properties. 25-180 micrometers is preferable, More preferably, it is 50-150 micrometers, More preferably, it is 100-130 micrometers.

  The adhesive film 12 is a layer having an adhesive function, and as a constituent material thereof, a thermoplastic resin and a thermosetting resin may be used in combination, or a thermoplastic resin may be used alone.

  The glass transition temperature of the adhesive film 12 is preferably in the range of 0 to 100 ° C, more preferably in the range of 10 to 80 ° C, and still more preferably 20 ° C to 60 ° C. When the glass transition temperature is 0 ° C. or higher, it is possible to prevent the tackiness of the adhesive film 12 in the B-stage state from being increased and the handling property from being lowered. Further, when the semiconductor wafer is diced, it is possible to prevent the adhesive melted by friction with the dicing blade from adhering to the semiconductor chip, thereby causing a pickup failure. On the other hand, by setting the glass transition temperature to 100 ° C. or lower, it is possible to prevent fluidity and adhesion with a semiconductor wafer from being lowered. Here, the glass transition temperature is a frequency of 10.0 Hz and a strain of 0.025% in a temperature range of −30 ° C. to 250 ° C. using a viscoelasticity measuring device (Rheometrics: model: RSA-II). This is the temperature at which Tan δ (G ″ (loss elastic modulus) / G ′ (storage elastic modulus)) shows a maximum value when measured under a temperature rising rate of 10 ° C./min.

  The tensile storage modulus of the adhesive film 12 at 23 ° C. before curing is preferably in the range of 50 to 5000 MPa, more preferably in the range of 100 to 3000 MPa, and still more preferably in the range of 300 to 2000 MPa. By setting the tensile storage elastic modulus of the adhesive film 12 to 50 MPa or more, generation of transfer marks on the adhesive film 12 can be more reliably suppressed. In addition, the sliding property of the adhesive film 12 is improved, and the occurrence of wrinkles when bonded to the cover film 2 can be more reliably suppressed. Moreover, adhesiveness with the semiconductor wafer mounted, the board | substrate to die-bond, etc. can be made favorable by the said tensile storage elastic modulus of the adhesive film 12 being 5000 Mpa or less. In the present invention, the tensile storage elastic modulus of the adhesive film means the tensile storage elastic modulus before thermosetting when the adhesive film is a thermosetting type.

  The value of the tensile storage modulus is determined by the following measurement method. That is, the adhesive composition solution is applied onto a release liner that has been subjected to a mold release treatment and dried to form an adhesive film 12 having a thickness of 100 μm. The adhesive film 12 is measured for a tensile storage elastic modulus at 23 ° C. before the adhesive film 12 is cured using a viscoelasticity measuring device (Rheometrics: model: RSA-II). More specifically, the sample size is 30.0 × length 5.0 × thickness 0.1 mm, the measurement sample is set in a film tensile measurement jig, and the frequency is in the temperature range of −30 ° C. to 280 ° C. The measurement is performed under the conditions of 10.0 Hz, a strain of 0.025%, and a heating rate of 10 ° C./min.

  The weight average molecular weight of the thermoplastic resin is preferably 300,000 or more and 150 or less, more preferably 350,000 to 1,000,000, and still more preferably 400,000 to 800,000. By setting the weight average molecular weight of the thermoplastic resin to 300,000 or more, the tensile storage modulus of the adhesive film at 23 ° C. can be controlled to a suitable value. In addition, when the thermoplastic resin has a weight average molecular weight of 300,000 or more and a relatively low molecular weight content, the contamination of a clean adherend can be prevented. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

  Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, heat Examples thereof include plastic polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins. These thermoplastic resins can be used alone or in combination of two or more. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor device is particularly preferable.

  The acrylic resin is not particularly limited, and includes one or two or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Examples include polymers as components. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, a cyclohexyl group, and 2-ethylhexyl. Group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, or dodecyl group.

  In addition, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Carboxyl group-containing monomers such as acid anhydride monomers such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- (meth) acrylic acid 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -Methyla Hydroxyl group-containing monomers such as relate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate or (meth) Examples thereof include sulfonic acid group-containing monomers such as acryloyloxynaphthalene sulfonic acid, and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate. Among these, a carboxyl group-containing monomer is preferable from the viewpoint of setting the tensile storage modulus of the die bond film to a suitable value.

  Examples of the thermosetting resin include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. These resins can be used alone or in combination of two or more. In particular, an epoxy resin containing a small amount of ionic impurities that corrode semiconductor chips is preferable. Moreover, as a hardening | curing agent of an epoxy resin, a phenol resin is preferable.

  The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type. , Biphenyl type, naphthalene type, fluorene type, phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., bifunctional epoxy resin or polyfunctional epoxy resin, or hydantoin type, trisglycidyl isocyanurate Type or glycidylamine type epoxy resin is used. These can be used alone or in combination of two or more. Of these epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins or tetraphenylolethane type epoxy resins are particularly preferred. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent and are excellent in heat resistance and the like.

  Further, the phenol resin acts as a curing agent for the epoxy resin. Examples include resol-type phenolic resins and polyoxystyrenes such as polyparaoxystyrene. These can be used alone or in combination of two or more. Of these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.

  The mixing ratio of the epoxy resin and the phenol resin is preferably such that, for example, the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of epoxy group in the epoxy resin component. More preferred is 0.8 to 1.2 equivalents. That is, if the blending ratio of both is out of the above range, sufficient curing reaction does not proceed and the properties of the cured epoxy resin are likely to deteriorate.

  In the present embodiment, the adhesive film 12 containing an epoxy resin, a phenol resin, and an acrylic resin is particularly preferable. Since these resins have few ionic impurities and high heat resistance, the reliability of the semiconductor chip can be ensured. In this case, the mixing ratio of the epoxy resin and the phenol resin is 10 to 200 parts by weight with respect to 100 parts by weight of the acrylic resin component.

  The adhesive film 12 may use a thermosetting catalyst as a constituent material of the adhesive film 12 as necessary. The blending ratio is preferably within the range of 0.1 to 3.0 parts by weight, more preferably within the range of 0.15 to 2.0 parts by weight, with respect to 100 parts by weight of the organic component, and 0.2 to 1. A range of 0 part by weight is particularly preferable. By setting the blending ratio to 0.1 parts by weight or more, the adhesive force after thermosetting can be favorably expressed. On the other hand, when the blending ratio is 3.0 parts by weight or less, it is possible to suppress a decrease in storage stability.

  The thermosetting catalyst is not particularly limited, and examples thereof include imidazole compounds, triphenylphosphine compounds, amine compounds, triphenylborane compounds, and trihalogenborane compounds. These can be used alone or in combination of two or more.

  Examples of the imidazole compound include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11Z), 2-heptadecylimidazole (trade name; C17Z), and 1,2-dimethylimidazole (product). Name: 1.2 DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1- Benzyl-2-methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2 -Undecylimidazole (trade name: C11Z-CN), 1-cyanoethyl 2-phenylimidazolium trimellitate (trade name; 2PZCNS-PW), 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine (trade name; 2MZ-A) ), 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine (trade name; C11Z-A), 2,4-diamino-6- [2'- Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name; 2E4MZ-A), 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl -S-triazine isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydride Carboxymethyl-methylimidazole (trade name; 2P4MHZ-PW), and the like (all made by Shikoku Kasei Co., Ltd.).

  The triphenylphosphine compound is not particularly limited, and examples thereof include triorganophosphines such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and diphenyltolylphosphine. Fin, tetraphenylphosphonium bromide (trade name; TPP-PB), methyltriphenylphosphonium (trade name; TPP-MB), methyltriphenylphosphonium chloride (trade name; TPP-MC), methoxymethyltriphenylphosphonium (trade name) ; TPP-MOC), benzyltriphenylphosphonium chloride (trade name; TPP-ZC) and the like (all manufactured by Hokuko Chemical Co., Ltd.). The triphenylphosphine compound is preferably substantially insoluble in the epoxy resin. It can suppress that thermosetting progresses too much that it is insoluble with respect to an epoxy resin. Examples of the thermosetting catalyst having a triphenylphosphine structure and substantially insoluble in the epoxy resin include methyltriphenylphosphonium (trade name: TPP-MB). The “insoluble” means that the thermosetting catalyst made of a triphenylphosphine compound is insoluble in a solvent made of an epoxy resin, and more specifically, a temperature range of 10 to 40 ° C. It means that 10% by weight or more does not dissolve.

  The triphenylborane compound is not particularly limited, and examples thereof include tri (p-methylphenyl) phosphine. The triphenylborane compound further includes those having a triphenylphosphine structure. The compound having the triphenylphosphine structure and the triphenylborane structure is not particularly limited. For example, tetraphenylphosphonium tetraphenylborate (trade name; TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name; (TPP-MK), benzyltriphenylphosphonium tetraphenylborate (trade name; TPP-ZK), triphenylphosphine triphenylborane (trade name; TPP-S), and the like (all manufactured by Hokuko Chemical Co., Ltd.).

  The amino compound is not particularly limited, and examples thereof include monoethanolamine trifluoroborate (manufactured by Stella Chemifa Corporation), dicyandiamide (manufactured by Nacalai Tesque Corporation), and the like.

  The trihalogen borane compound is not particularly limited, and examples thereof include trichloroborane.

  Since the adhesive film 12 according to the present embodiment is crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer may be added as a crosslinking agent during production. . Thereby, the adhesive property under high temperature is improved and heat resistance is improved.

  A conventionally well-known thing can be employ | adopted as said crosslinking agent. In particular, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, adducts of polyhydric alcohol and diisocyanate are more preferable. The addition amount of the crosslinking agent is usually preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of the polymer. When the amount of the cross-linking agent is more than 7 parts by weight, the adhesive force is lowered, which is not preferable. On the other hand, if it is less than 0.05 parts by weight, the cohesive force is insufficient, which is not preferable. Moreover, you may make it include other polyfunctional compounds, such as an epoxy resin, together with such a polyisocyanate compound as needed.

  Moreover, an inorganic filler can be suitably mix | blended with the adhesive film 12 according to the use. The blending of the inorganic filler makes it possible to impart conductivity, improve thermal conductivity, adjust the elastic modulus, and the like. Examples of the inorganic filler include silica, clay, gypsum, calcium carbonate, barium sulfate, alumina oxide, beryllium oxide, silicon carbide, silicon nitride and other ceramics, aluminum, copper, silver, gold, nickel, chromium, bell And various inorganic powders made of metals such as tin, zinc, palladium, solder, or alloys, and other carbons. These can be used alone or in combination of two or more. Among these, silica, particularly a melting strength is preferably used. Moreover, it is preferable that the average particle diameter of an inorganic filler exists in the range of 0.01-80 micrometers.

  The blending amount of the inorganic filler is preferably set to 0 to 80 parts by weight and more preferably set to 0 to 70 parts by weight with respect to 100 parts by weight of the organic component.

  The adhesive film 12 can be appropriately mixed with other additives as necessary. Examples of other additives include flame retardants, silane coupling agents, ion trapping agents, and the like. Examples of the flame retardant include antimony trioxide, antimony pentoxide, brominated epoxy resin, and the like. These can be used alone or in combination of two or more. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like. These compounds can be used alone or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and bismuth hydroxide. These can be used alone or in combination of two or more.

  Although the thickness of the adhesive film 12 is not specifically limited, For example, it is about 5-100 micrometers, Preferably it is about 5-70 micrometers.

  The film 10 for a semiconductor device can have an antistatic ability. As a result, it is possible to prevent the circuit from being broken due to the generation of static electricity during the bonding and peeling, and the resulting charging of the semiconductor wafer or the like. The antistatic ability is imparted by adding an antistatic agent or a conductive material to the base material 13, the pressure-sensitive adhesive layer 14 or the adhesive film 12, and providing a conductive layer made of a charge transfer complex or a metal film on the base material 13. Etc., etc. As these methods, a method in which impurity ions that may change the quality of the semiconductor wafer are less likely to be generated is preferable. As a conductive substance (conductive filler) blended for the purpose of imparting conductivity and improving thermal conductivity, spherical, needle-like, and flaky shapes such as silver, aluminum, gold, copper, nickel, and conductive alloys Examples thereof include metal powders, metal oxides such as alumina, amorphous carbon black, and graphite. However, it is preferable that the adhesive film 12 is non-conductive because it can be prevented from electrically leaking.

  The adhesive film 12 is protected by the cover film 2. The cover film 2 has a function as a protective material that protects the adhesive film 12 until it is put into practical use. The cover film 2 is peeled off when a semiconductor wafer is stuck on the adhesive film 12 of the adhesive film with a dicing sheet. As the cover film 2, a plastic film or paper surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, a fluorine-type release agent, or a long-chain alkyl acrylate-type release agent can be used.

  The tensile storage elastic modulus Eb of the cover film 2 is preferably in the range of 1 to 5000 MPa, more preferably in the range of 50 to 4500 MPa, and still more preferably in the range of 100 to 4000 MPa. By setting the tensile storage modulus Eb of the cover film 2 to 1 MPa or more, the followability of the cover film 2 to the die bond film 12 can be further improved. Further, by setting the tensile storage elastic modulus Eb of the cover film 2 to 5000 MPa or less, the cover film 2 can be further prevented from being folded when the adhesive film 12 is bonded to the cover film 2, It is possible to prevent the adhesive film 12 from being damaged or air bubbles from being mixed between the films.

  The thickness of the cover film 2 is preferably 10 to 100 μm, more preferably 15 to 75 μm, and further preferably 25 to 50 μm from the viewpoints of workability and transportability.

Next, the manufacturing method of the film 10 for semiconductor devices which concerns on this Embodiment is demonstrated below.
In the method for manufacturing the semiconductor device film 10 according to the present embodiment, the adhesive layer 14 is formed on the substrate 13 to form the dicing film 11, and the adhesive film 12 is formed on the substrate separator 22. A step, a step of punching the adhesive film 12 in accordance with the shape of the semiconductor wafer to be attached, a step of laminating the adhesive layer 14 of the dicing film 11 and the adhesive film 12 as a bonding surface, and a circular shape corresponding to the ring frame A step of punching the dicing film 11 on, a step of producing the adhesive film 1 with a dicing sheet by peeling the substrate separator 22 on the adhesive film 12, and a dicing sheet with a predetermined interval on the cover film 2 And a step of bonding the adhesive film 1 together.

  The manufacturing process of the dicing film 11 is performed as follows, for example. First, the base material 13 can be formed by a conventionally known film forming method. Examples of the film forming method include a calendar film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method.

  Next, after a pressure-sensitive adhesive composition solution is applied onto the substrate 13 to form a coating film, the coating film is dried under predetermined conditions (heat-crosslinked as necessary) to form a pressure-sensitive adhesive layer 14. Form. It does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. Further, the drying conditions can be appropriately set according to the thickness and material of the coating film. Specifically, for example, the drying temperature is 80 to 150 ° C. and the drying time is 0.5 to 5 minutes. Moreover, after apply | coating an adhesive composition on the 1st separator 21 and forming a coating film, the coating film may be dried on the said drying conditions, and the adhesive layer 14 may be formed. Thereafter, the pressure-sensitive adhesive layer 14 is bonded to the base material 13 together with the first separator 21. Thereby, the dicing film 11 by which the adhesive layer 14 was protected by the 1st separator 21 is produced (refer Fig.3 (a)). The produced dicing film 11 may have a long form wound in a roll shape. In this case, it is preferable to wind the dicing film 11 while applying a tensile tension in the longitudinal direction or the width direction so that no slack, winding deviation, or positional deviation occurs. However, by applying a tensile tension, the dicing film 11 is wound into a roll shape with a residual tensile strain remaining. In addition, although the dicing film 11 may be extended | stretched when the said tension | tensile_strength is added at the time of winding of the dicing film 11, winding up does not aim at extending | stretching operation.

When the pressure-sensitive adhesive layer 14 is made of an ultraviolet-curing pressure-sensitive adhesive and is ultraviolet-cured in advance, it is formed as follows. That is, after an ultraviolet curable pressure-sensitive adhesive composition is applied onto the substrate 13 to form a coating film, the coating film is dried under a predetermined condition (heat-crosslinked as necessary) to form a pressure-sensitive adhesive layer. Form. The coating method, coating conditions, and drying conditions can be performed in the same manner as described above. Alternatively, an ultraviolet curable pressure-sensitive adhesive composition may be applied onto the first separator 21 to form a coating film, and then the coating film may be dried under the drying conditions to form a pressure-sensitive adhesive layer. Thereafter, the pressure-sensitive adhesive layer is transferred onto the substrate 13. Further, the adhesive layer is irradiated with ultraviolet rays under predetermined conditions. No particular limitation is imposed on the irradiation conditions of the ultraviolet ray usually is preferably within the range of accumulated light quantity is 30~1000mJ / cm ^2, more preferably within the range of a 50 to 800 mJ / cm ^2, and 100 to 500 mJ / cm ² More preferably within the range. The cumulative amount of light by adjusting within the numerical range, it is possible to control the release force _{F 2} between the adhesive film 12 and the dicing film 11 in the range of 0.08~10N / 100mm. When the irradiation with ultraviolet rays is less than 30 mJ / cm ² , the pressure-sensitive adhesive layer 14 may be insufficiently cured, and the peeling force from the adhesive film 12 may be excessively increased. As a result, the adhesiveness with the adhesive film is increased, and the pickup property is lowered. Further, adhesive residue may occur on the adhesive film after pickup. On the other hand, when the integrated light quantity exceeds 1000 mJ / cm ² , the peeling force from the adhesive film 12 may be too small. As a result, interface peeling may occur between the pressure-sensitive adhesive layer 14 and the adhesive film 12. As a result, chip skipping may occur during dicing of the semiconductor wafer. In addition, the base material 13 may be thermally damaged. Furthermore, the curing of the pressure-sensitive adhesive layer 14 proceeds excessively, the tensile elastic modulus becomes too large, and the expandability decreases. In addition, you may perform irradiation of an ultraviolet-ray after the bonding process with the below-mentioned adhesive film 12. FIG. In this case, the ultraviolet irradiation is preferably performed from the substrate 13 side.

  The production process of the adhesive film 12 is performed as follows. That is, an adhesive composition solution for forming the adhesive film 12 is applied on the base separator 22 so as to have a predetermined thickness, thereby forming a coating film. Thereafter, the coating film is dried under predetermined conditions to form the adhesive film 12. It does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. Further, the drying conditions can be appropriately set according to the thickness and material of the coating film. Specifically, for example, the drying is performed within a range of 70 to 160 ° C. and a drying time of 1 to 5 minutes. Moreover, after apply | coating an adhesive composition on the 2nd separator 23 and forming a coating film, the coating film may be dried on the said drying conditions, and the adhesive film 12 may be formed. Thereafter, the adhesive film 12 is bonded together with the second separator 23 on the substrate separator 22. Thereby, the laminated | multilayer film by which the adhesive film 12 and the 2nd separator 23 were laminated | stacked sequentially on the base-material separator 22 are produced (refer FIG.3 (b)). This laminated film may have a long form wound in a roll shape. In this case, it is preferable to wind the adhesive film 12 while applying a tensile tension in the longitudinal direction or the width direction so that the adhesive film 12 is not loosened, wound or misaligned.

  Next, the adhesive film 12 is punched in accordance with the shape of the semiconductor wafer to be attached, and is attached to the dicing film 11. Thereby, the adhesive film 1 with a dicing sheet is obtained. That is, the first separator 21 is peeled off from the dicing film 11 and the second separator 23 is peeled off from the punched adhesive film 12 so that the adhesive film 12 and the pressure-sensitive adhesive layer 14 are bonded to each other. Paste together (see FIG. 3C). At this time, pressure bonding is performed on at least one of the dicing film 11 and the adhesive film 12 while applying a tensile tension to the peripheral edge. Moreover, when the dicing film 11 is the long thing wound by roll shape, it is preferable to convey without applying tensile tension as much as possible with respect to the dicing film 11 in the longitudinal direction. This is to suppress the residual tensile strain of the film. However, from the viewpoint of preventing the dicing film 11 from generating slack, winding deviation, position deviation, void (bubble), etc., tensile tension may be applied within a range of 10 to 25N. Within this range, even if tensile residual strain remains in the dicing film 11, it is possible to prevent the occurrence of interface peeling between the dicing film 11 and the adhesive film 12.

The dicing film 11 and the adhesive film 12 can be bonded together by, for example, pressure bonding. At this time, the lamination temperature is not particularly limited, but is usually preferably 30 to 80 ° C, more preferably 30 to 60 ° C, and particularly preferably 30 to 50 ° C. Moreover, although a linear pressure is not specifically limited, Usually, 0.1-20 kgf / cm is preferable and 1-10 kgf / cm is more preferable. By laminating the laminating temperature and / or the linear pressure within the numerical range for the adhesive film 12 in which the glass transition temperature of the organic component is within the range of −20 to 50 ° C., and bonding the dicing film 11 together. , it is possible to control the release force _{F 2} between the adhesive film 12 and the dicing film 11 in the range of 0.08~10N / 100mm. Here, for example, by increasing the lamination temperature in the range, it is possible to increase the peel force F ₂ between the dicing film 11 and the adhesive film 12. Also, by increasing the linear pressure within the range, it is possible to increase the peel force F _2.

  Next, the base material separator 22 on the adhesive film 12 is peeled off, and the cover film 2 is bonded while applying tensile tension. Subsequently, the dicing film 11 is punched out into a circular shape corresponding to the ring frame at a predetermined interval. Thereby, the film 10 for semiconductor devices by which the pre-cut adhesive film 1 with a dicing sheet was laminated | stacked on the cover film 2 at predetermined intervals is produced.

The bonding of the adhesive film 12 to the cover film 2 in the adhesive film with dicing sheet 1 is preferably performed by pressure bonding. At this time, the lamination temperature is not particularly limited, but is usually preferably 20 to 80 ° C, more preferably 20 to 60 ° C, and particularly preferably 20 to 50 ° C. Moreover, although a linear pressure is not specifically limited, Usually, 0.1-20 kgf / cm is preferable and 0.2-10 kgf / cm is more preferable. For the adhesive film 12 in which the glass transition temperature of the organic component is within the range of −20 to 50 ° C., the laminating temperature and / or the linear pressure are adjusted within the numerical range, respectively, and bonded to the cover film 2. The peeling force F ₁ between the adhesive film 12 and the cover film 2 can be controlled within a range of 0.025 to 0.075 N / 100 mm. Here, for example, by increasing the laminating temperature within the above range, it is possible to increase the peeling force F ₁ between the adhesive film with dicing sheet 1 and the cover film 2. Also, by increasing the linear pressure within the range, it is possible to increase the peel force F _1. Moreover, it is preferable to convey with respect to the cover film 2, applying tension tension in the longitudinal direction as much as possible. This is for suppressing the tensile residual strain of the cover film 2. However, from the viewpoint of preventing the cover film 2 from generating slack, winding deviation, position deviation, void (bubble), etc., a tensile tension may be applied within a range of 10 to 25N. If it is in the said range, even if the tensile residual distortion remains in the cover film 2, it can prevent that the film floating phenomenon of the cover film 2 with respect to the adhesive film 1 with a dicing sheet generate | occur | produces.

  The first separator 21 bonded on the pressure-sensitive adhesive layer 14 of the dicing film 11, the substrate separator 22 of the adhesive film 12, and the second separator 23 bonded on the adhesive film 12 are not particularly limited. A conventionally known release-treated film can be used. The first separator 21 and the second separator 23 each have a function as a protective material. The substrate separator 22 has a function as a substrate when the adhesive film 12 is transferred onto the pressure-sensitive adhesive layer 14 of the dicing film 11. The material constituting each of these films is not particularly limited, and conventionally known materials can be employed. Specifically, for example, polyethylene terephthalate (PET), polyethylene, polypropylene, a plastic film or paper surface-coated with a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate release agent can be used.

  The adhesive film of the present invention can be used as a die bond film or a flip chip type semiconductor back film. The flip chip type semiconductor back film is used for forming on the back surface of a semiconductor element (for example, a semiconductor chip) flip-chip connected to an adherend (for example, various substrates such as a lead frame and a circuit board). Is.

  Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in this example are not intended to limit the gist of the present invention only to those unless otherwise limited. The term “parts” means parts by weight.

Example 1
(Preparation of adhesive layer for dicing film)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 76 parts of 2-ethylhexyl acrylate (2EHA), 24 parts of 2-hydroxyethyl acrylate (HEA), and benzoyl peroxide 0 .2 parts and 60 parts of toluene were added and polymerized in a nitrogen stream at 61 ° C. for 6 hours to obtain an acrylic polymer A having a weight average molecular weight of 750,000. The molar ratio of 2EHA to HEA was 100 mol to 20 mol. The measurement of a weight average molecular weight is as above-mentioned.

  To this acrylic polymer A, 10 parts of 2-methacryloyloxyethyl isocyanate (hereinafter referred to as “MOI”) (80 mol% with respect to HEA) was added, and an addition reaction treatment was performed at 50 ° C. for 48 hours in an air stream. An acrylic polymer A ′ was obtained.

  Next, with respect to 100 parts of acrylic polymer A ′, 6 parts of an isocyanate crosslinking agent (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and a photopolymerization initiator (trade name “Irgacure 651”, Ciba 4 parts) (manufactured by Specialty Chemicals) was added to prepare an adhesive solution.

  The pressure-sensitive adhesive solution prepared above was applied on the surface of the PET release liner (first separator) that had been subjected to silicone treatment, and heat-crosslinked at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 30 μm. Next, a low-density polyethylene resin (Sumitomo Chemical Sumikasen F218) was extruded by the T-die method to prepare a sheet-like base material having a thickness of 40 μm, and bonded to the surface of the pressure-sensitive adhesive layer. Thereafter, it was stored at 50 ° C. for 24 hours.

  Further, the PET release liner was peeled off, and ultraviolet rays were directly irradiated only on the portion (circular shape with a diameter of 220 mm) corresponding to the adhesive layer of the semiconductor wafer (circular shape with a diameter of 200 mm). This produced the dicing film concerning a present Example. The irradiation conditions are as follows.

<Ultraviolet irradiation conditions>
Ultraviolet (UV) irradiation apparatus: high pressure mercury lamp UV irradiation integrated light quantity: 500 mJ / cm ²
Output: 120W
Irradiation intensity: 200 mW / cm ²

<Preparation of adhesive film>
Epoxy resin 1 (manufactured by JER Corporation, Epicoat 1004) 228 parts, epoxy resin 2 (manufactured by JER Corporation) with respect to 100 parts of acrylic rubber having an epoxy group ("SG80H"; manufactured by Nagase ChemteX Corporation) , Epicoat 827) 206 parts, phenol resin (Mitsui Chemicals Co., Ltd., Milex XLC-4L) 466 parts, spherical silica (manufactured by Admatex Co., Ltd., trade name; SO-25R, average particle size 0) 0.5 μm) and 667 parts of a curing catalyst (C11-Z, manufactured by Shikoku Kasei Co., Ltd.) were dissolved in methyl ethyl ketone and adjusted to a concentration of 25% by weight. The tensile storage modulus of the adhesive film at 23 ° C. was 1421 MPa, and the glass transition temperature was 41.5 ° C.

  This adhesive composition solution is applied onto a release-treated film (base separator) with a fountain coater to form a coating layer, and hot air at 150 ° C. and 10 m / s is directly applied to the coating layer for 2 minutes. Sprayed and dried. Thus, an adhesive film having a thickness of 25 μm was produced on the release treatment film. As the release treatment film (base separator), a polyethylene terephthalate film (thickness 50 μm) subjected to silicone release treatment was used.

<Production of adhesive film with dicing sheet>
Next, the adhesive film was cut into a circular shape having a diameter of 230 mm, and the pressure-sensitive adhesive layer of the dicing film and the adhesive film cut into a circular shape were bonded together. A nip roll is used for the bonding, and the bonding conditions are a lamination temperature of 50 ° C. and a linear pressure of 3 kgf / cm. Further, the base separator on the adhesive film is peeled off to form a release treatment film (cover film). A release-treated polyethylene terephthalate film (thickness 50 μm) was bonded. At this time, in order to prevent misalignment, voids (bubbles), etc. on the cover film, a linear pressure is applied without applying a lamination temperature while applying a tensile tension of 17 N in the MD direction using a dancer roll. Bonding was performed at 2 kgf / cm to prepare an adhesive film with a dicing sheet.

<Preparation of film for semiconductor device>
Furthermore, the film for a semiconductor device according to this example, in which 250 dicing sheet-attached adhesive films were bonded to each other at a distance of 10 mm by punching the dicing film into a circular shape having a diameter of 270 mm so that the adhesive film is at the center. Got.

(Example 2)
<Production of dicing film>
The dicing film according to this example was the same as in Example 1 except that a 100 μm polyolefin film (base material) was bonded to the pressure-sensitive adhesive layer.

<Preparation of adhesive film>
For 100 parts of an acrylic ester polymer (trade name; Paraclone W-197CM, Tg: 18 ° C., weight average molecular weight: 400,000) manufactured by Negami Kogyo Co., Ltd. containing ethyl acrylate-methyl methacrylate as a main component, Epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1027) 434 parts, phenol resin (Mitsui Chemicals Co., Ltd., Millex XLC-4L) 466 parts, spherical silica as an inorganic filler (Admatex Co., Ltd.) ), Trade name: SO-25R, average particle size 0.5 μm) 1500 parts, curing catalyst (Shikoku Kasei Co., Ltd., C11-Z) 3 parts dissolved in methyl ethyl ketone to a concentration of 20% by weight. It was adjusted. The tensile storage modulus of the adhesive film at 23 ° C. was 517 MPa, and the glass transition temperature was 47.5 ° C.

  This adhesive composition solution is applied onto a release-treated film (base separator) with a fountain coater to form a coating layer, and hot air at 150 ° C. and 10 m / s is directly applied to the coating layer for 2 minutes. Sprayed and dried. Thus, an adhesive film having a thickness of 25 μm was produced on the release treatment film. As the release treatment film (base separator), a polyethylene terephthalate film (thickness 50 μm) subjected to silicone release treatment was used.

<Production of adhesive film with dicing sheet>
The adhesive film was cut into a circular shape having a diameter of 230 mm, and the pressure-sensitive adhesive layer of the dicing film was bonded to the adhesive film cut into a circular shape. Furthermore, the substrate separator on the adhesive film was peeled off, and a silicone release-treated polyolefin film (thickness 25 μm) was bonded as a release-treated film (cover film) to produce an adhesive film with a dicing sheet. . The bonding conditions were the same as in Example 1.

<Preparation of film for semiconductor device>
Furthermore, the film for a semiconductor device according to this example in which 250 dicing sheet-attached adhesive films were bonded to each other at a distance of 100 mm by punching the dicing film into a circular shape having a diameter of 270 mm so that the adhesive film is centered. Got.

Example 3
<Production of dicing film>
The dicing film according to the present example, except that an adhesive tape base material (thickness 100 μm) made only of random polypropylene resin (MFR: 2 g / 10 min, ethylene component content: 60% by weight) was used as the adhesive layer. The same one as in Example 1 was used. In addition, the corona treatment was given to one surface of the adhesive tape base material. Next, a polyolefin film (base material) having a thickness of 100 μm was bonded to the surface of the pressure-sensitive adhesive layer. Thereafter, it was stored at 50 ° C. for 24 hours.

<Preparation of adhesive film>
For 100 parts of acrylic rubber (manufactured by Nagase ChemteX Corporation, trade name: SG-708-6), 434 parts of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1027), phenol resin ( 466 parts of Mitsui Chemicals Co., Ltd., Millex XLC-LL), 429 parts of spherical silica (manufactured by Admatechs Co., Ltd., trade name: SO-25R, average particle size 0.5 μm) as an inorganic filler are dissolved in methyl ethyl ketone. The concentration was adjusted to 25% by weight. The tensile storage modulus of the adhesive film at 23 ° C. was 2320 MPa, and the glass transition temperature was 38.9 ° C.

  This adhesive composition solution is applied onto a release-treated film (base separator) with a fountain coater to form a coating layer, and hot air at 150 ° C. and 10 m / s is directly applied to the coating layer for 2 minutes. Sprayed and dried. Thus, an adhesive film having a thickness of 25 μm was produced on the release treatment film. As the release treatment film (base separator), a polyethylene terephthalate film (thickness 50 μm) subjected to silicone release treatment was used.

<Production of adhesive film with dicing sheet>
The adhesive film was cut into a circular shape having a diameter of 230 mm, and the pressure-sensitive adhesive layer of the dicing film was bonded to the adhesive film cut into a circular shape. Further, the substrate separator on the adhesive film is peeled off to form a release treatment film (cover film), and a low-density polyethylene resin (Sumitomo Chemical F218) is extruded by the T-die method to form a sheet having a thickness of 25 μm. By bonding together, an adhesive film with a dicing sheet was produced. The bonding conditions were the same as in Example 1.

<Preparation of film for semiconductor device>
Furthermore, the film for a semiconductor device according to this example, in which 250 dicing sheet-attached adhesive films were bonded to each other at a distance of 10 mm by punching the dicing film into a circular shape having a diameter of 270 mm so that the adhesive film is at the center. Got.

(Comparative Example 1)
<Preparation of film for semiconductor device>
A film for a semiconductor device according to this comparative example was produced in the same manner as in Example 1, except that a polyethylene terephthalate film having a silicone release treatment having a thickness of 100 μm was used as the cover film.

(Comparative Example 2)
<Production of dicing film>
The dicing film according to this comparative example is an example except that 130 μm of an adhesive tape base material made only of a random polypropylene resin (MFR: 1.7 g / 10 minutes, ethylene component content: 75% by weight) was used as an adhesive layer. 1 was used.

<Preparation of adhesive film>
The adhesive film similar to Example 3 was used as the adhesive film according to this comparative example.

<Production of adhesive film with dicing sheet>
The adhesive film was cut into a circular shape having a diameter of 230 mm, and the pressure-sensitive adhesive layer of the dicing film was bonded to the adhesive film cut into a circular shape. Furthermore, the base film separator on the adhesive film was peeled off, and a 25 μm-thick polyolefin release-treated polyolefin film was bonded as a release-treated film (cover film) to produce an adhesive film with a dicing sheet. The bonding conditions were the same as in Example 1.

<Preparation of film for semiconductor device>
Furthermore, the film for a semiconductor device according to this comparative example in which 250 dicing sheet-attached adhesive films are bonded to each other by punching the dicing film into a circular shape having a diameter of 270 mm so that the adhesive film is centered. Got.

(Tensile storage modulus Ea of dicing film at 23 ° C.)
The dicing film in each Example and Comparative Example was measured for tensile storage elastic modulus at 23 ° C. before curing of the dicing film using a viscoelasticity measuring device (Rheometrics Corporation: model: RSA-II). More specifically, a measurement sample having a length of 30.0 mm × a width of 5.0 mm and a cross-sectional area of 0.125 to 0.9 mm ² is set on a film tension measuring jig, and is in a temperature range of −30 ° C. to 100 ° C. The measurement was performed under the conditions of a frequency of 10.0 Hz, a strain of 0.025%, and a heating rate of 10 ° C./min.

(Tensile storage modulus Eb of cover film at 23 ° C.)
About the cover film of each Example and the comparative example, the tensile elasticity modulus in 23 degreeC was measured using the viscoelasticity measuring apparatus (Rheometrics company_made: type | formula: RSA-II). More specifically, the sample size is 30 mm long × 5 mm wide, the measurement sample is set in a film tensile measurement jig, and the frequency is 1.0 Hz, the strain is 0.025%, and the temperature is raised in the temperature range of −30 to 280 ° C. The measurement was performed at a speed of 10 ° C./min.

(Tensile storage modulus of adhesive film at 23 ° C.)
About the adhesive film of each Example and the comparative example, the tensile elasticity modulus in 23 degreeC was measured using the viscoelasticity measuring apparatus (Rheometrics company_made: type | formula: RSA-II). More specifically, the sample size is 30 mm long × 5 mm wide, the measurement sample is set in a film tensile measurement jig, and the frequency is 10.0 Hz, the strain is 0.025%, and the temperature is raised in the temperature range of −30 to 280 ° C. The measurement was performed at a speed of 10 ° C./min.

(Glass-transition temperature)
The glass transition temperature of each Example and Comparative Example was 10.0 Hz with a frequency of 0.0 Hz in a temperature range of −30 ° C. to 250 ° C. using a viscoelasticity measuring device (Rheometrics, model: RSA-II). The temperature at which Tan δ (G ″ (loss elastic modulus) / G ′ (storage elastic modulus)) when measured under the conditions of 025% and a heating rate of 10 ° C./min was the maximum value.

(Evaluation of pickup)
The cover film was peeled off from each film for a semiconductor device, and a semiconductor wafer was mounted on the adhesive film. A semiconductor wafer having a size of 8 inches and a thickness of 75 μm was used. The semiconductor wafer mounting conditions were the same as described above.

  Next, the semiconductor wafer was diced according to the following conditions to form 30 semiconductor chips. Furthermore, the semiconductor chip was picked up together with the die bond film. The pick-up was performed on 30 semiconductor chips (5 mm long × 5 mm wide), and the success rate was calculated by counting the cases where the semiconductor chip was successfully picked up without breakage. The results are shown in Table 1 below. The pickup conditions are as follows.

<Dicing conditions>
Dicing method: Step cut Dicing device: DISCO DFD6361 (trade name, manufactured by DISCO Corporation)
Dicing speed: 50mm / sec
Dicing blade: Z1; “NBC-ZH203O-SE27HDD” manufactured by Disco Corporation
Z2: “NBC-ZH203O-SE27HBB” manufactured by Disco Corporation
Dicing blade rotation speed: Z1; 50,000 rpm, Z2; 50,000 rpm
Dicing tape cutting depth: 20μm
Wafer chip size: 5mm x 5mm

<Pickup conditions>
Pickup device: Product name “SPA-300” manufactured by Shinkawa Co., Ltd. Number of needles: 5 Push-up amount: 400 μm
Push-up speed: 10 mm / sec.

<Evaluation of the presence or absence of voids by transfer of traces after freezing storage>
The film for a semiconductor device obtained in each Example and Comparative Example was wound into a roll shape with a winding tension of 2 kg. And in this state, it was left to stand in a refrigerator at a temperature of −30 ° C. for 2 weeks. Then, after returning to room temperature, the roll was unwound, the semiconductor wafer was mounted using the 100th adhesive film with a dicing sheet, and the presence or absence of voids was confirmed visually. A semiconductor wafer having a size of 8 inches and a thickness of 75 μm was used. The bonding conditions were as follows. The results are shown in Table 1.

<Bonding conditions>
Pasting device: ACC Co., Ltd., trade name: RM-300
Pasting speed: 20 mm / sec Pasting pressure: 0.25 MPa
Pasting temperature: 60 ° C

<Transportability with automatic pasting machine>
Using MA-3000III manufactured by Nitto Seiki Co., Ltd., an adhesive film with a dicing sheet was attached to 100 wafers, and the number of troubles that caused the apparatus to pause was measured. The pasting conditions were a pasting speed of 20 mm / sec, a pasting pressure: 0.25 MPa, and a pasting temperature: 60 ° C.

<Hygroscopic reliability evaluation>
The film for a semiconductor device used in the frozen storage test was mounted, diced, and picked up under the above conditions. Next, the semiconductor element was die-bonded to a bismaleimide-triazine resin substrate under conditions of 120 ° C. × 500 gf × 1 sec, and then subjected to a thermal history at 180 ° C. for 1 hour. Next, these were molded using a molding machine (manufactured by TOWA, Model-Y-series). Specifically, an epoxy-based sealing resin (manufactured by Nitto Denko, HC-300B6) was used and molded at 175 ° C. with a preheating setting of 3 seconds, an injection time of 12 seconds, and a curing time of 120 seconds. Then, it heat-hardened on 175 degreeC and the conditions for 5 hours, and obtained the semiconductor package. This package was subjected to moisture absorption treatment in a thermo-hygrostat (30 ° C., 60% RH) for 192 hours, and then repeatedly inserted into an IR reflow apparatus SAI-2604M (manufactured by Senju Metal Industry) three times. The package surface peak temperature at that time was adjusted to 260 ° C. The presence or absence of peeling was observed with an ultrasonic exploration imaging device (FS-200, manufactured by Hitachi Construction Machinery Finetech), then the center of the package was cut, the cut surface was polished, and then packaged using a Keyence optical microscope. The cross section was observed, and the case where peeling was not recognized was rated as ◯, and the case where peeling was observed was marked as x.

(result)
As is apparent from Table 1, the film for semiconductor device production of Examples 1, 2, and 3 was not confirmed to have voids due to winding transfer even when stored in a freezer at a temperature of −30 ° C. for 2 weeks. Further, there was no trouble in conveyance with the apparatus, the mountability, the dicing property, and the pickup property were good, and no peeling was observed in the moisture absorption reliability test.
On the other hand, in the film for a semiconductor device of Comparative Example 1, the film lift of the cover film and the film were broken at the time of mounting the semiconductor wafer. Further, when stored in a freezer at a temperature of −30 ° C. for 2 weeks, voids due to winding marks were confirmed. Further, when a moisture absorption reliability test was performed on the film transferred with the trace, voids due to the trace transfer were confirmed.
In the film for a semiconductor device of Comparative Example 2, voids due to trace transfer were confirmed when stored in a freezer for 2 weeks. In addition, the success rate of pickup was 100%, but chip skipping occurred. Further, when a moisture absorption reliability test was performed on the film transferred with the trace, voids due to the trace transfer were confirmed.

DESCRIPTION OF SYMBOLS 1 Adhesive film with a dicing sheet 2 Cover film 10 Film for semiconductor devices 11 Dicing film 12 Adhesive film 13 Base material 14 Adhesive layer 21 First separator 22 Base material separator 23 Second separator

Claims (6)

A film for a semiconductor device in which an adhesive film with a dicing sheet in which an adhesive film is laminated on a dicing film is laminated on a cover film at a predetermined interval,
A film for a semiconductor device, wherein a ratio Ea / Eb of a tensile storage elastic modulus Ea of a dicing film at 23 ° C. and a tensile storage elastic modulus Eb of a cover film at 23 ° C. is within a range of 0.001 to 100. .   2. The semiconductor according to claim 1, wherein the adhesive film has a glass transition temperature in the range of 0 to 100 ° C. and a tensile storage elastic modulus at 23 ° C. before curing of 50 MPa to 5000 MPa. Film for equipment.   The film for a semiconductor device according to claim 1, wherein the cover film has a thickness of 10 to 100 μm.   The thickness of the said dicing film is 25-180 micrometers, The film for semiconductor devices of any one of Claims 1-3 characterized by the above-mentioned.   The film for a semiconductor device according to claim 1, wherein a tensile storage elastic modulus Ea of the dicing film at 23 ° C. is 1 to 500 MPa.   The film for a semiconductor device according to claim 1, wherein a tensile storage elastic modulus Eb of the cover film at 23 ° C. is 1 to 5000 MPa.

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