JP2010031183A - Energy ray hardening type chip protecting film - Google Patents

Abstract

An object of the present invention is to provide a highly reliable energy ray-curable chip protection film having high hardness and excellent adhesion to a chip.
The energy ray curable chip protecting film of the present invention comprises (A) a binder polymer component, (B) a cationic polymerization type curable component, (C) a cationic photopolymerization initiator, and (D) a radical polymerization. An energy ray curable protective film forming layer comprising a mold curable component and (E) a radical photopolymerization initiator.
[Selection] Figure 1

Description

  The present invention relates to an energy beam curable chip protecting film, and more particularly to an energy beam curable chip protecting film for protecting the back surface of a semiconductor chip mounted in a face down manner.

In recent years, as a mounting technology for semiconductor elements such as integrated circuits, WL-CSP (Wafer Level Chip Size Package), which is packaged in a wafer state before dicing and is cut into chips at the final stage, has been put into practical use. Progressing. WL-CSP has the characteristics of being small, thin, and high speed because it is almost the same size as a bare chip and has a short wiring length, and is adopted as a CSP for mobile phones, for example.

In such WL-CSP, a tape substrate with bumps is used as a semiconductor package substrate (also referred to as rewiring or Interposer), and bumps formed on the tape substrate and bumps formed on the circuit formation surface of the semiconductor wafer. And are connected directly. At this time, the semiconductor wafer is mounted on the tape substrate by a so-called face-down method in which the circuit formation surface faces the tape substrate.
The tape substrate on which the semiconductor wafer is mounted is cut (diced) in units of chips by a dicing saw, whereby a CSP having the same size as the semiconductor chip can be obtained.

  In the CSP as described above, the back surface of the chip is not sealed with resin and is exposed to the outside. Therefore, various chip protection films have been proposed to protect and reinforce the back surface of the chip. The film for chip protection also has a function of suppressing chipping during dicing by being attached to the back surface of the wafer before dicing.

  For example, Patent Document 1 discloses a protective film for a chip having a release sheet, a protective film forming layer formed of a thermosetting component or energy ray curable component formed on the release surface of the release sheet, and a binder polymer. A forming sheet is disclosed. In Patent Document 1, the protective film forming layer of the chip protective film forming sheet is attached to the back surface of the semiconductor wafer, the release sheet is peeled off from the protective film forming layer, and then the protective film forming layer is cured by heating or irradiation with energy rays. Then, a protective film is formed on the entire surface of the wafer. Thereby, since the strength is improved as compared with the case of the wafer alone, damage to the wafer during handling is reduced.

Patent Document 2 discloses a protective film-forming sheet for chips having a curable protective film composed of a thermosetting component and / or an energy ray-curable component, as in Patent Document 1, and further includes protection. Add fillers, pigments, dyes, etc. to the protective film forming layer for the purpose of improving the strength and hardness of the film, improving mark recognition when performing laser marking such as product number on the protective film, and improving the appearance. Is disclosed.
JP 2004-260190 A JP 2004-214288 A

  As described in Patent Documents 1 and 2, the method of curing the protective film includes a method of heating and curing the protective film forming layer containing a thermosetting component, and a protection containing an energy ray curable component. There is a method of curing the film forming layer by irradiation with energy rays.

  In general, heat curing requires heat treatment at 100 to 200 ° C. for about 1 to 3 hours. In the case of such thermosetting, since the protective film forming layer is slowly cured while flowing, a protective film having excellent adhesion to the chip and high hardness can be obtained. However, thermosetting has a problem that processing time is long and workability and productivity are poor.

  On the other hand, in energy ray curing, for example, ultraviolet rays can be instantly cured in about 10 to 300 seconds, and the processing time is much shorter than heat curing, and the workability and productivity are excellent. It is also advantageous in that it is not damaged by heat and the curing equipment is compact. However, when adding fillers, pigments, dyes, etc. to the protective film forming layer for the purpose of improving the laser mark visibility and improving the appearance, it is difficult to transmit energy rays, compared with the case of thermosetting. It is difficult to fully cure the entire film. Further, in the energy ray curing, the protective film forming layer is instantaneously cured, so that there is a problem that the cured protective film has low adhesion to the chip and is easily peeled off.

  Accordingly, an object of the present invention is to provide a highly reliable energy ray-curable chip protecting film having high hardness and excellent adhesion to a chip.

  As a result of intensive studies on the above problems, the present inventors have used a cationic polymerization type curable component and a radical polymerization type curable component having different curing mechanisms in combination with a chip while having high hardness. The inventors have found that an energy ray curable chip protecting film having excellent adhesion can be obtained, and have completed the present invention.

  That is, the first aspect of the present invention includes (A) a binder polymer component, (B) a cationic polymerization type curable component, (C) a cationic photopolymerization initiator, (D) a radical polymerization type curable component, And (E) an energy beam curable chip protecting film comprising an energy beam curable protective film forming layer containing a radical photopolymerization initiator.

  According to a second aspect of the present invention, in the energy ray-curable chip protecting film according to the first aspect, the radical photopolymerization initiator (E) absorbs light in a long wavelength region of 350 nm or more. It is a polymerization initiator.

  According to a third aspect of the present invention, in the energy ray-curable chip protecting film according to the first or second aspect, the radical photopolymerization initiator (E) is an acylphosphine oxide. To do.

According to a fourth aspect of the present invention, in the energy ray-curable chip protecting film according to the third aspect, the radical photopolymerization initiator (E) is represented by the following structural formula (1): It is 4,6-trimethylbenzoyl diphenylphosphine oxide.

Structural formula (1)

  According to a fifth aspect of the present invention, in the energy ray-curable chip protecting film according to any one of the first to fourth aspects, the cationic polymerization type curable component (B) is an epoxy resin. It is characterized by.

  According to a sixth aspect of the present invention, in the energy ray-curable chip protecting film according to any one of the first to fifth aspects, the radical polymerization type curable component (D) is an epoxy acrylate. It is characterized by.

  According to a seventh aspect of the present invention, in the energy ray curable chip protecting film according to any one of the first to sixth aspects, the cationic polymerization type curable component (B) and the radical polymerization type curing are used. The compounding ratio with the sex component (D) is 30:70 to 70:30 in mass ratio.

  According to an eighth aspect of the present invention, in the energy ray curable chip protecting film according to any one of the first to seventh aspects, a release sheet is further provided on one or both sides of the energy ray curable protective film forming layer. It is characterized by having.

  A ninth aspect of the present invention is a dicing tape-integrated chip protection film in which a dicing tape is bonded to the energy ray-curable chip protection film according to any one of the first to eighth aspects.

  According to the present invention, by using a cationic polymerization type curable component and a radical polymerization type curable component having different curing mechanisms in combination, the chip protection has high hardness and excellent adhesion to the chip. A film can be realized.

Embodiments of the present invention will be described below with reference to the drawings.
FIG.1 and FIG.2 shows two examples of the energy ray hardening-type chip | tip protective film of this invention which has a protective film formation layer on a peeling sheet. FIG. 1 shows a configuration in which the release sheet 1 is temporarily attached to both surfaces of the protective film forming layer 2, and FIG. 2 shows a configuration in which the release sheet 1 is temporarily attached to one surface of the protective film forming layer 2.
Below, the structure of a peeling sheet and a protective film formation layer is demonstrated. Moreover, the manufacturing method and usage method of this chip protection film will also be described.

<Peeling sheet>
The release sheet 1 is used for the purpose of improving the handleability of the film for protecting a chip and for the purpose of protecting the protective film forming layer 2.
Examples of release sheets include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polypinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, and polyurethane. Film, ethylene / vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A resin film or the like is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient.

  In particular, when the release sheet is peeled after the protective film forming layer is cured, a polymethylpentene film, a polyethylene terephthalate film, or a polyimide film excellent in heat resistance can be suitably used.

  The surface tension of the release sheet is preferably 40 mN / m or less, and more preferably 35 mN / m or less. Such a release sheet having a low surface tension can be obtained by appropriately selecting the material, and can also be obtained by applying a silicone resin or the like to the surface of the sheet and performing a release treatment.

  The thickness of the release sheet is usually about 5 to 300 μm, preferably about 10 to 200 μm, and particularly preferably about 20 to 150 μm.

<Protective film forming layer>
The energy ray curable protective film forming layer 2 is cured by irradiation with energy rays such as ultraviolet rays and electron beams, and forms a protective film on the back surface of the chip. This energy ray curable protective film forming layer 2 comprises (A) a binder polymer component, (B) a cationic polymerization type curable component, (C) a cationic photopolymerization initiator, and (D) a radical polymerization type curable component. And (E) a radical photopolymerization initiator as an essential component. Furthermore, you may contain (F) dye and / or a pigment, (G) filler, and (H) other components as needed. These components will be described below.

(A) Binder polymer component In this invention, in order to improve the flexibility and operativity as a film, a polymer component is used. As the polymer component, for example, an acrylic copolymer, a polyester resin, a urethane resin, a silicone resin, a rubber polymer, or the like can be used, and an acrylic copolymer having a polymerizable double bond is particularly preferable. The weight average molecular weight of the acrylic copolymer is preferably 50,000 or more, particularly preferably in the range of 200,000 to 1,000,000. If the molecular weight is too low, sheet formation will be insufficient, and if it is too high, compatibility with other components will deteriorate, resulting in hindering film formation.

(B) Cationic polymerization type curable component The cationic polymerization type curable component is a compound that undergoes cationic polymerization upon irradiation with energy rays and is cured. As such a compound, an epoxy resin can be suitably used, and an alicyclic epoxy resin having a high cationic polymerizability is particularly preferable. An epoxy resin is used in combination with a cationic photopolymerization initiator that generates an acid upon irradiation with energy rays, whereby an epoxy group efficiently undergoes ring-opening polymerization. In general, the cationic polymerization type curable component has a slower reaction rate than the radical polymerization type curable component, and thus the progress of the reaction tends to be insufficient, and the hardness is difficult to obtain. Excellent adhesion to. Therefore, by using a cationic polymerization type curable component, it is possible to express excellent adhesiveness in energy ray curing that is conventionally inferior in adhesiveness to a chip as compared with thermosetting.

(C) Cationic Photopolymerization Initiator The cationic photopolymerization initiator generates an acid that becomes a reactive species by irradiation with energy rays, and sequentially advances the polymerization process. By adding a cationic photopolymerization initiator to the cationic polymerization type curable component, the polymerization curing time and the amount of light irradiation can be reduced.
The amount of the cationic photopolymerization initiator used is preferably about 1 to 10 parts by mass with respect to 100 parts by mass in total of the cationic polymerization type curable components.

  As the cationic photopolymerization initiator, aromatic diazonium salts, aromatic iodonium salts and the like can be preferably used.

(D) Radical polymerization type curable component The radical polymerization type curable component is a compound that is radically polymerized and cured by irradiation with energy rays. In general, since radical polymerization type curable compounds have a high reaction rate and stress due to curing shrinkage, as described above, the adhesion to the chip is inferior to that of cationic polymerization type curable compounds. By using it in combination with a radical polymerization photoinitiator that generates radicals, it can be efficiently polymerized and cured, and a protective film with high hardness can be formed by energy ray curing.

  The radical polymerization type curable component has at least one polymerizable double bond in the molecule and has a weight average molecular weight in the range of 100 to 30,000, more preferably in the range of 300 to 10,000. For example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1,4-butylene glycol diacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, polyester or polyether type urethane acrylate oligomer, polyester acrylate , Polyether acrylate, epoxy acrylate.

  Among these, an ultraviolet curable resin is particularly preferable. Specifically, epoxy acrylate, urethane acrylate oligomer, oligoester acrylate, and the like are preferable, and epoxy acrylate is particularly preferable in terms of hardness, heat resistance, adhesiveness, and the like.

  The blending ratio of the cationic polymerization type curable component (B) and the radical polymerization type curable component (D) is not particularly limited, but is preferably 30:70 to 70:30 in mass ratio. If this mass ratio bias is too large, that is, if the mass ratio of the cationic polymerization type curable component (B) is too large, the adhesiveness is lowered, while the mass ratio of the radical polymerization type curable component (D). If is too large, the hardness will decrease. Then, the protective film which has hardness and adhesiveness can be obtained by mix | blending in said ratio.

(E) Radical-based photopolymerization initiator The radical-based photopolymerization initiator generates a radical that becomes a reactive species by irradiation with energy rays, and initiates a radical reaction. By adding a radical photopolymerization initiator to the radical polymerization type curable component, the polymerization curing time and the amount of light irradiation can be reduced.
The amount of the radical photopolymerization initiator used is preferably about 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of the energy ray curable components.

  As radical photopolymerization initiators, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4-diethylthiol Xanthone, α-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, β-chloranthraquinone, acylphosphine oxide and the like can be mentioned.

Among these, an acylphosphine oxide that absorbs light in a long wavelength region of 350 nm or more and is curable even in a system to which a dye and a pigment are added is particularly preferable. As the acylphosphine oxide, it is particularly preferable to use 2,4,6-trimethylbenzoyldiphenylphosphine oxide represented by the following structural formula (1).
Structural formula (1)

(F) Dye and Pigment The energy ray curable protective film forming layer 2 may be colored. The protective film forming layer 2 is colored by blending pigments, dyes and the like. By coloring the protective film forming layer 2, it is possible to improve the mark recognizability and the appearance when the protective film forming layer 2 is subjected to laser marking such as a product number. Examples of such pigments include carbon black and various inorganic pigments. Also, various organic pigments such as azo, indanthrene, indophenol, phthalocyanine, indigoid, nitroso, xanthene, oxyketone and the like can be mentioned.

  The amount of these additives varies depending on the type, but is 0.1 to 10 mass with respect to a total of 100 parts by mass of the binder polymer component, the cationic polymerization type curable component, the radical polymerization type curable component, and the filler. Parts, preferably about 0.5 to 3 parts by mass. Moreover, in order to adjust the cohesive force before hardening, crosslinking agents, such as an organic polyvalent isocyanate compound, an organic polyvalent imine compound, and an organometallic chelate compound, can also be added.

(G) Filler Examples of the filler include silica such as crystalline silica and synthetic silica, and inorganic filler such as alumina and glass balloon. By adding an inorganic filler to the protective film forming layer 2, the hardness of the protective film forming layer 2 can be improved. In addition, the thermal expansion coefficient of the protective film after curing can be brought close to the thermal expansion coefficient of the wafer, thereby reducing the warpage of the wafer during processing. Synthetic silica is preferable as the filler, and in particular, synthetic silica of the type from which the α-ray source that causes malfunction of the semiconductor device is removed as much as possible is optimal. As the shape of the filler, any of a spherical shape, a needle shape, and an amorphous type can be used, but a spherical filler capable of closest packing is particularly preferable.

  Moreover, as a filler added to the protective film formation layer 2, the following functional fillers other than the inorganic filler mentioned above may be mix | blended. For example, for the purpose of imparting conductivity after die bonding, a conductive filler such as gold, silver, copper, nickel, aluminum, stainless steel, carbon, or ceramic, or nickel, aluminum, etc. coated with silver is added. In addition, for the purpose of imparting thermal conductivity, a metal material such as gold, silver, copper, nickel, aluminum, stainless steel, silicon, germanium, or a thermal conductive material such as an alloy thereof may be added.

  The amount of filler added to the protective film forming layer 2 varies depending on the type of filler, but the binder polymer component, radical polymerization type curable component, cationic polymerization type curable component, and filler total 100 parts by mass. On the other hand, 30 to 85 parts by mass, preferably about 50 to 75 parts by mass is appropriate. The pencil hardness after curing can be adjusted by adding the filler in the protective film forming layer 2 at such a blending ratio and irradiating with energy rays. Further, the thermal expansion coefficient of the protective film after curing can be brought close to the thermal expansion coefficient of the wafer.

(H) Other components In addition to the above-described components, the protective film forming layer 2 may include a butadiene-based rubber as a crosslinking agent, a coupling agent, an antistatic agent, an antioxidant, a flame retardant, and a stress relaxation agent as necessary. Or silicone rubber or the like.

  A crosslinking agent is for adjusting the cohesive force before hardening, and an organic polyvalent isocyanate compound, an organic polyvalent imine compound, an organometallic chelate compound, etc. are mentioned.

  The coupling agent improves adhesion and adhesion without impairing the heat resistance of the cured film, and also improves water resistance (moisture heat resistance). The coupling agent is preferably a silane (silane coupling agent) from the viewpoint of versatility and cost.

  The thickness of the protective film forming layer 2 is preferably 5 to 200 μm, and more preferably 10 to 50 μm. If it is too thin, it is difficult to obtain the chip protection and reinforcing effects, and problems such as uneven color are likely to occur. Moreover, when too thick, it will become difficult to harden the whole film by energy ray irradiation.

<Manufacturing method>
Next, an example of a method for producing the energy ray curable chip protecting film of the present invention will be described.
The energy ray curable chip protecting film of the present invention comprises a roll knife coater, a gravure coater, a die coat containing a composition comprising each component constituting the energy ray curable protective film forming layer 2 on the release surface of a release sheet. It can be obtained by coating or drying directly or by transfer according to a generally known method such as a coater or a reverse coater. If necessary, the above composition may be dissolved or dispersed in a solvent and applied.

<How to use>
The use application of the energy ray curable chip protection film of the present invention is not particularly limited as long as it is a chip protection application. For example, it can be used for a chip back surface protection application for WL-CSP.
The usage method of the film in the case of applying the energy ray curable chip protecting film of the present invention to the chip back surface protection for WL-CSP will be described with reference to FIGS. First, in a state where the film for chip protection is heated and pressurized at 40 ° C. or higher and 0.05 to 0.5 MPa, the energy ray curable protective film forming layer 2 is bonded to the back surface of the wafer W, and the film is made to the wafer size. Disconnect. Next, as shown in FIG. 3, the film bonded to the wafer W is irradiated with 100 to 2000 mJ / cm ² of ultraviolet rays from the release sheet 1 side using the UV lamp 5. Thereby, the cationic polymerization reaction and the radical polymerization reaction proceed simultaneously, and the protective film forming layer 2 is cured. As described above, by using a cationic polymerization type curable component and a radical polymerization type curable component having different curing mechanisms in combination, a protective film having high hardness and excellent adhesion on the back surface of the wafer W. Can be formed.

  Thereafter, the release sheet 1 is peeled off, and as shown in FIG. 4, a protective film forming layer 2 (protective film) obtained by curing the dicing tape 6 composed of the base film 8 and the adhesive layer 7 formed on the base film 8 is used. ) And dicing the protective film together with the wafer W. Finally, the dicing tape 6 is irradiated with ultraviolet rays to reduce its adhesiveness, and the chip protected with the protective film of the present invention can be obtained by picking up the UV-diced chip with a pickup means such as a collet. it can.

<Dicing tape integrated chip protection film>
Next, the dicing tape-integrated chip protecting film in which the energy ray curable chip protecting film of the present invention and the dicing tape are integrated will be described.
FIG. 5 is a cross-sectional view showing an example of a dicing tape-integrated chip protection film. As shown in the figure, the dicing tape-integrated chip protection film has a protective film forming layer 2 that has been cut in advance to the size of a wafer, and a dicing tape 6 composed of an adhesive layer 7 and a base film 8. . The protective film forming layer 2 may be the same size as the dicing tape 6, but using the protective film forming layer 2 that has been cut according to the size of the wafer in advance becomes a ring frame used in the dicing process. This is preferable in that it is difficult to cause the problem of adhesive residue.

  Thus, according to the structure which integrated the film for chip protection and the dicing tape used at the dicing process of a wafer, the bonding process of a protective film and the bonding process of a dicing tape can be performed in one process. In addition, since the energy ray irradiation process of the chip protection film and the dicing tape can be performed in one process, the process can be simplified and the productivity can be improved.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a following example.

(Examples 1-4 and Comparative Examples 1-3)
A coating solution for a curable protective film forming layer was prepared by blending each component shown in Table 1.
In addition, all the units of the numerical values in Table 1 are parts by mass. Moreover, the code | symbol of each component in Table 1 is as follows.

A: Polymer component (acrylic copolymer having a weight average molecular weight of 800,000 and a glass transition temperature of 10 ° C.)
B: Cationic polymerization type curable component (alicyclic epoxy resin)
C1: Cationic photopolymerization initiator 1 (aromatic diazonium salt)
C2: Cationic photopolymerization initiator 2 (aromatic iodonium salt)
D: Radical polymerization type curable component (epoxy acrylate resin (bis A type))
E1: Radical photoinitiator 1 (2,2-dimethoxy-2-phenylacetophenone absorption wavelength 252 nm)
E2: radical photopolymerization initiator 2 (2,4,6-trimethylbenzoyldiphenylphosphine oxide (acylphosphine oxide type))
F: Dye and pigment (black pigment (azo), carbon black)
G: Filler (spherical synthetic silica, average particle size 1.2 μm)

  Next, after coating and drying each of the above coating solutions on a release sheet made of a polyethylene terephthalate (PET) film having a thickness of 38 μm at 130 ° C./3 minutes so that the dry film thickness becomes 25 μm, Another release sheet same as the above was bonded on top to prepare an energy beam curable chip protecting film having a three-layer structure comprising release sheet / energy ray curable protective film forming layer / release sheet.

  About each energy ray hardening type chip | tip protective film, the pencil hardness of the energy ray hardening type protective film formation layer was measured with the following method. In addition, mounting reliability and adhesion to the wafer were examined by the following methods. These results are also shown in Table 1.

<Pencil hardness>
The energy ray curable protective film-forming layer was bonded to a silicon wafer, and ultraviolet rays were irradiated at 1,000 mJ / cm ² using an ultraviolet irradiator (illuminance of 40 mW / cm ² for 25 seconds). Then, the pencil hardness of the protective film formation layer hardened | cured at room temperature (25 degreeC) based on JIS standard: K5600-5-4 was measured.

<Mounting reliability>
The energy ray curable protective film-forming layer was bonded to a silicon wafer, and ultraviolet rays were irradiated at 1,000 mJ / cm ² using an ultraviolet irradiator (illuminance of 40 mW / cm ² for 25 seconds). Thereafter, a dicing tape was bonded to the protective film forming layer side and diced to 10 mm × 10 mm. Each divided silicon chip was treated in a constant temperature and humidity chamber of 85 ° C./85% RH for 168 hours, and then heated in an IR reflow furnace at 250 ° C./120 seconds. Then, the presence or absence of peeling between the obtained silicon chip and the protective film was observed with SAT (ultrasonic imaging device: manufactured by Hitachi Construction Machinery Finetech Co., Ltd.). Of the 20 samples, those in which peeling occurred were counted.

<Adhesion test>
The energy ray curable protective film-forming layer was bonded to a silicon wafer, and ultraviolet rays were irradiated at 1,000 mJ / cm ² using an ultraviolet irradiator (illuminance of 40 mW / cm ² for 25 seconds). A 1 mm × 1 mm square cut was made on the film surface (half cut using a dicer). The cellophane tape was tightly attached to the place where the grid was formed, and the end of the tape was rapidly peeled off at an angle of 45 ° to observe the state of the grid. When the film of 1 mm × 1 mm was peeled off by 70% or more, ×, 5 to 70% were Δ, and 5% or less were ○.

  In Examples 1 to 4 of the present invention, since a cationic polymerization type curable component and a radical polymerization type curable component having different curing mechanisms are used in combination, pencil hardness H or higher is achieved and excellent mounting is achieved. It was confirmed to show reliability and adhesion.

  On the other hand, Comparative Examples 1 and 2 did not include a cationic polymerization type curable component, and thus mounting reliability and adhesion were insufficient. Moreover, in the comparative example 3, since the radical curing type curable component was not mix | blended, hardness was inadequate. This is because the cationic polymerization type curable component has a slow reaction rate, and since it is black, the degree of transmission of energy rays to the inside is low, the reaction proceeds easily, and hardness is difficult to obtain. It is considered a thing. In addition, it is considered that the radical polymerization type curable component has a high reaction rate, so that stress due to curing shrinkage is increased and adhesion is hardly obtained.

It is sectional drawing which shows an example of the energy ray hardening-type chip | tip protective film of this invention. It is sectional drawing which shows the other example of the energy ray hardening-type chip | tip protective film of this invention. It is sectional drawing explaining the hardening method of the energy ray hardening-type chip | tip protective film of this invention. It is sectional drawing for demonstrating the dicing method of the wafer with a film for chip protection of the present invention. It is sectional drawing which shows an example of the dicing tape integrated chip protection film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Release sheet 2 Energy-beam curable protective film formation layer 5 UV lamp 6 Dicing tape 7 Adhesive 8 Base material

Claims (9)

  (A) a binder polymer component, (B) a cationic polymerization type curable component, (C) a cationic photopolymerization initiator, (D) a radical polymerization type curable component, and (E) a radical photopolymerization initiator. An energy beam-curable chip protecting film comprising an energy beam-curable protective film-forming layer.   2. The energy ray-curable chip protecting film according to claim 1, wherein the radical photopolymerization initiator (E) is a photopolymerization initiator that absorbs light in a long wavelength region of 350 nm or more.   3. The energy ray-curable chip protecting film according to claim 1, wherein the radical photopolymerization initiator (E) is an acylphosphine oxide. 4. The energy ray-curable type according to claim 3, wherein the radical photopolymerization initiator (E) is 2,4,6-trimethylbenzoyldiphenylphosphine oxide represented by the following structural formula (1). Chip protection film.

Structural formula (1)
  The energy ray-curable chip protection film according to any one of claims 1 to 4, wherein the cationic polymerization type curable component (B) is an epoxy resin.   6. The energy ray-curable chip protection film according to claim 1, wherein the radical polymerization type curable component (D) is an epoxy acrylate.   The blending ratio of the cationic polymerization type curable component (B) and the radical polymerization type curable component (D) is 30:70 to 70:30 by mass ratio. The energy ray-curable chip protecting film according to claim 6.   The energy ray-curable chip protecting film according to any one of claims 1 to 7, further comprising a release sheet on one side or both sides of the energy ray-curable protective film forming layer. A dicing tape-integrated chip protection film in which a dicing tape is bonded to the energy ray-curable chip protection film according to any one of claims 1 to 8.