TW201742151A - Composite sheet for forming protective film, method for producing semiconductor chip with protective film, and method for producing semiconductor device - Google Patents

Abstract

A composite sheet for forming protective film, including an energy ray curable film for forming protective film provided on a support sheet, wherein the support sheet has a light shielding layer in a region in the vicinity of the peripheral edge portion of the support sheet.

Description

Composite film for forming protective film, method for producing semiconductor wafer with protective film, and method for manufacturing semiconductor device

The present invention relates to a method of manufacturing a semiconductor wafer with a protective film and a method of manufacturing a semiconductor device.

The priority of Japanese Patent Application No. 2016-092012, filed on Jan. 28,,,,,,,,,,,,,

In recent years, the industry has manufactured semiconductor devices using a mounting method called a so-called face down method. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to the substrate. Therefore, there is a case where the back surface of the semiconductor wafer opposite to the circuit surface is exposed.

There will be organic materials on the back side of the bare semiconductor wafer. The resin film of the material is used as a protective film to be incorporated into a semiconductor device in the form of a semiconductor wafer with a protective film.

The protective film is used to prevent cracking of the semiconductor wafer after the cutting step or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film having a film for forming a protective film for forming a protective film on a support sheet is used. In the composite sheet for forming a protective film, a protective film can be formed by curing the film for forming a protective film, and the support sheet can be used as a dicing sheet, whereby the film for forming a protective film can be formed integrally with a dicing sheet. A composite sheet for forming a protective film.

In the composite sheet for forming a protective film, for example, a composite sheet for forming a protective film having a film for forming a protective film having thermosetting properties is mainly used, and the film for forming a thermosetting protective film is formed by curing by heating. Protective film. In this case, for example, the back surface of the semiconductor wafer (the surface opposite to the surface on which the electrode is formed) is bonded to the film for forming a protective film by a thermosetting protective film, and then the protective film is formed by heating. The film is cured by a film to form a protective film, and the semiconductor wafer is formed by dividing the semiconductor wafer together with the protective film by dicing. Then, the semiconductor wafer is directly attached to the support sheet while being attached to the protective film, and is picked up. Further, the curing and cutting of the film for forming a protective film may be performed in the reverse order of the above.

However, since the heat curing of the film for forming a thermosetting protective film usually takes about several hours, it is desirable to shorten the curing time. In view of the above, the industry is investigating a film for forming a protective film which can be cured by irradiation with an energy ray such as ultraviolet rays for forming a protective film. For example, an energy ray-curable protective film formed on a release film (see Patent Document 1) and an energy ray-curable wafer protective film which can form a protective film having high hardness and excellent adhesion to a semiconductor wafer (see Patent) Literature 2).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5144433.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-031183.

However, when a semiconductor wafer with a protective film is produced by using the energy ray-curable protective film forming film disclosed in Patent Document 1 and Patent Document 2, it is sometimes impossible to pick up a specific one. The semiconductor wafer of the film causes poor pickup.

Accordingly, an object of the present invention is to provide a semiconductor wafer with a protective film, a method of manufacturing a semiconductor device, and a composite sheet for forming a protective film which can be used in the above-described manufacturing method, and the semiconductor wafer with the protective film can use an energy ray Curable film for protective film formation with protection The semiconductor wafer of the film suppresses pickup defects when it is picked up.

In order to solve the above problems, the inventors of the present invention conducted intensive studies and found the following. In the case of manufacturing a semiconductor wafer with a protective film by using an energy ray-curable film for forming a protective film, when a semiconductor wafer is attached to a film for forming a protective film, the film for forming a protective film may be used in the film for forming a protective film. A region where the semiconductor wafer is not attached to a region farther from the semiconductor wafer than the outer periphery of the semiconductor wafer (that is, the outer side of the region where the semiconductor wafer is attached to the film for forming a protective film) is generated. However, when the film for forming a protective film is cured by irradiating the energy ray, the region where the semiconductor wafer is attached to the film for forming a protective film and the region where the semiconductor wafer is not attached to the outer periphery of the semiconductor wafer The two regions irradiate the energy rays to harden the film for forming a protective film. Further, the inventors of the present invention have found that the cause of the poor adhesion and the pickup failure is that the film for forming a protective film (that is, the film for forming a protective film) including the region farther from the semiconductor wafer than the outer periphery of the semiconductor wafer The area on the outer side of the region to which the semiconductor wafer is attached is hardened.

The composite sheet for forming a protective film of the present invention is obtained by providing a film for forming a protective film having an energy ray-curable property on a support sheet, and the support sheet has a light-shielding layer in a region in the vicinity of the peripheral portion.

In the composite sheet for forming a protective film of the present invention, the light shielding layer may be composed of a printing layer.

Manufacture of a semiconductor wafer with a protective film in one aspect of the invention The method of cutting a semiconductor wafer in a laminate of a protective film for forming a support sheet and an energy ray-curable film and a semiconductor wafer, and then forming a film for the protective film, except for the peripheral portion. In the film for forming a protective film other than the vicinity, a portion of the attachment region of the semiconductor wafer is irradiated with an energy ray, and a semiconductor wafer with a protective film is formed on the support sheet, and the semiconductor wafer with the protective film is picked up.

A method for producing a semiconductor wafer with a protective film according to another aspect of the present invention is as follows: a protective film for forming a protective film for forming a support sheet or an energy ray-curable layer, and a laminate of a semiconductor wafer, and the protective film are provided. In the film for forming a protective film, except for the region in the vicinity of the peripheral portion, the portion of the adhesion region of the semiconductor wafer is irradiated with an energy ray, and the semiconductor wafer is diced to form a protective film on the support sheet. The semiconductor wafer is picked up by the semiconductor wafer with the protective film attached thereto.

In the method for producing a semiconductor wafer with a protective film according to the present invention, the support sheet may have a light shielding layer in a region in the vicinity of the peripheral portion.

In the method for producing a semiconductor wafer with a protective film according to the present invention, the protective film forming film may be irradiated with an energy ray via a shielding plate in a portion of the semiconductor wafer in a region other than a region in the vicinity of the peripheral portion.

In the method of manufacturing a semiconductor device of the present invention, the semiconductor wafer with a protective film obtained by the method for producing a semiconductor wafer with a protective film according to any one of the above is connected to the substrate.

That is, the present invention encompasses the following aspects.

[1] A composite sheet for forming a protective film, comprising a film for forming a protective film having an energy ray-curable property on a support sheet, wherein the support sheet has a light-shielding layer in a region in the vicinity of the peripheral portion.

[2] The composite sheet for forming a protective film according to [1], wherein the light shielding layer is composed of a printed layer.

[3] A method of manufacturing a semiconductor wafer with a protective film, comprising: the semiconductor wafer in a laminate of a protective film for forming a support sheet, an energy ray-curable layer, and a semiconductor wafer; The film for forming a protective film is diced, and an energy ray is applied to a portion of the film for forming a protective film that is diced except for a region in the vicinity of the peripheral portion, thereby forming an attached surface on the support sheet. a semiconductor wafer of a protective film; and picking up the aforementioned semiconductor wafer with a protective film.

[4] A method of producing a semiconductor wafer with a protective film, comprising: forming a protective film for a protective film forming film and a semiconductor wafer in which a support sheet, an energy ray-curable protective film, and a semiconductor wafer are sequentially provided; The portion of the film in which the semiconductor wafer is attached to the region other than the region near the peripheral portion is irradiated with an energy ray; after the illuminating the energy ray, the semiconductor wafer is diced, and a semiconductor wafer with a protective film is formed on the support sheet; The semiconductor wafer with the aforementioned protective film is picked up.

[5] The method for producing a semiconductor wafer with a protective film according to [3] or [4], wherein the support sheet has a light shielding layer in a region in the vicinity of the peripheral portion. .

[6] The method for producing a semiconductor wafer with a protective film according to [3] or [4], wherein the film for the protective film is not included in the semiconductor wafer except for a region in the vicinity of the peripheral portion. The attached area partially illuminates the energy line through the shielding plate.

[7] A semiconductor wafer with a protective film obtained by the method for producing a semiconductor wafer with a protective film according to any one of [3] to [6], Connected to the substrate.

According to the present invention, there is provided a semiconductor wafer with a protective film, a method of manufacturing a semiconductor device, and a composite sheet for forming a protective film for use in the above-described manufacturing method, wherein the semiconductor wafer with a protective film can be used for energy ray hardening. The film for protective film formation is manufactured by manufacturing a semiconductor wafer with a protective film, and picking up is suppressed at the time of picking up.

1A, 1B, 1C, 1D, 1E‧‧‧ Composite film for protective film formation

2F‧‧‧Protective film forming sheet

10‧‧‧Support tablets

10a‧‧‧ (supported) surface

11‧‧‧Substrate

11a‧‧‧ (substrate) surface

12‧‧‧Adhesive layer

12a‧‧‧ (adhesive layer) surface

13, 23‧‧‧film for protective film formation

13', 23'‧‧‧ protective film

13a, 23a‧‧‧ (film for protective film formation)

13b‧‧‧ (the other one of the films for forming a protective film, which is opposite to the other surface)

15‧‧‧Release film

15'‧‧‧First peel film

15"‧‧‧Second release film

16‧‧‧Layer layer for fixtures

16a‧‧‧ (adhesive layer for the fixture) surface

17‧‧‧ ring frame

18‧‧‧Semiconductor wafer

19‧‧‧Semiconductor wafer

20‧‧‧Cutting Blade

21‧‧‧Energy line irradiation device

24‧‧‧ shading layer

Fig. 1 is a cross-sectional view showing an embodiment of a composite sheet for forming a protective film of the present invention in a schematic manner.

Fig. 2 is a view showing the back surface of the composite sheet for forming a protective film of Fig. 1.

Fig. 3 is a cross-sectional view showing another embodiment of the composite sheet for forming a protective film of the present invention in a schematic manner.

Fig. 4 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 5 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 6 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 7 is a cross-sectional view showing an embodiment of a sheet for forming a protective film which can be used in the method for producing a semiconductor wafer with a protective film of the present invention.

Fig. 8 is a schematic view showing an embodiment of a method of manufacturing a semiconductor wafer with a protective film of the present invention.

Fig. 9 is a schematic view showing another embodiment of a method for producing a semiconductor wafer with a protective film of the present invention.

复合Protective film forming composite sheet

The composite sheet for forming a protective film of the present invention comprises an energy-curable protective film forming film on the support sheet, and the support sheet has a light-shielding layer in a region in the vicinity of the peripheral portion of the support sheet.

In the present specification, the "film for forming a protective film" means a film for forming a protective film before curing, and the term "protective film" means a film obtained by curing a film for forming a protective film.

In the present specification, the term "energy line" means an electromagnetic wave or a charged particle beam having an energy quantum; and examples of the energy line include ultraviolet rays, radiation, an electron beam, and the like.

For example, a high-pressure mercury lamp, a Fusion H-type lamp, a xenon lamp, a black light lamp, or an LED (Light-Emitting Diode) lamp can be used as the ultraviolet light source. The electron beam can illuminate an electron beam generated by an electron beam accelerator or the like.

In the present specification, the term "energy ray hardenability" means a property of being hardened by irradiation with an energy ray, and "non-energy ray hardenability" means a property that does not harden even when irradiated with an energy ray.

The film for forming a protective film is cured by irradiation with an energy ray to form a protective film. The protective film serves to protect the back surface of the semiconductor wafer or the semiconductor wafer (the surface opposite to the electrode forming surface). The film for forming a protective film is soft and can be easily attached to an attached object. For example, the tensile modulus (Young's modulus) of the film for forming a protective film is about 1 × 10 ⁶ Pa to about 1 × 10 ⁸ Pa.

On the other hand, the tensile modulus (Young's modulus) of the protective film obtained by irradiating the energy-sensitive film to the film for forming a protective film is hardened to about 1×10 ⁸ Pa to 5.4×10 ⁹ Pa.

The tensile modulus (Young's modulus) of the protective film obtained by irradiating the energy-shielding film of the film for forming a protective film of the present invention is 1 × 10 ⁸ Pa or more, preferably 1.3 × 10 ⁸ Pa or more, more preferably 1.6 × 10 ⁸ Pa or more, particularly preferably 1.9 × 10 ⁸ Pa or more. When the tensile modulus of the protective film is at least the above lower limit value, the effect of suppressing the occurrence of the pin-out of the pin in the protective film is increased.

On the other hand, the upper limit of the tensile modulus of the protective film is not particularly limited, and may be, for example, any of 6 × 10 ⁹ Pa, 5.7 × 10 ⁹ Pa, and 5.4 × 10 ⁹ Pa.

That is, as one aspect of the tensile modulus of the protective film, it is 1 × 10 ⁸ Pa to 6 × 10 ⁹ Pa, preferably 1.3 × 10 ⁸ Pa to 5.7 × 10 ⁹ Pa, more preferably 1.6 ×. 10 ⁸ Pa to 5.7 × 10 ⁹ Pa, particularly preferably 1.9 × 10 ⁸ Pa to 5.4 × 10 ⁹ Pa.

Further, the tensile modulus (Young's modulus) of the film for forming a protective film and the protective film can be measured by the method described in the examples below.

The composite film for forming a protective film of the present invention is attached to a semiconductor wafer in a method for producing a semiconductor wafer with a protective film to be described later, and is provided with a film for forming a protective film having a support sheet and an energy ray-curable layer. (1) dicing the semiconductor wafer, and illuminating the adhesion region of the semiconductor wafer except for the region near the peripheral portion of the film for forming a protective film. After the line or (2) irradiates the energy line, the semiconductor wafer is diced to form a semiconductor wafer with a protective film on the support sheet, and the laminated body is extended, and the semiconductor wafer with the protective film is subjected to Pick up.

In this case, in the film for forming a protective film, a region where the semiconductor wafer is attached and a region where the semiconductor wafer is not attached to a region farther from the semiconductor wafer than the outer periphery of the semiconductor wafer (for example, a protective film) A region outside the region where the semiconductor wafer is attached to the film for formation). In the composite sheet for forming a protective film of the present invention, it is preferable that the support sheet has a light-shielding layer in a region in the vicinity of the peripheral portion of the support sheet in the vicinity of the peripheral portion of the support sheet. Therefore, when the film for forming a protective film is cured by irradiating the energy ray, the region where the semiconductor wafer is attached to the film for forming a protective film In the middle, the energy line is irradiated and the aforementioned region is well hardened. On the other hand, in the film for forming a protective film, a region in which the semiconductor wafer is not attached to the outer periphery (surrounding) of the semiconductor wafer, and a region in the vicinity of the peripheral portion of the support sheet (for example, a film for forming a protective film is attached) In the semiconductor wafer, the outer region of the region where the semiconductor wafer is bonded to the film for forming a protective film, and the region in the region in the vicinity of the peripheral portion of the support sheet is covered, the energy line is shielded to form an uncured region.

In this manner, in the case where the entire surface of the film for forming a protective film is irradiated with an energy ray, and the entire film for forming a protective film is cured, an unhardened region exists in a region where the semiconductor wafer is not attached to the film for forming a protective film. Thereby, the effect of extending the laminate body over the semiconductor wafer is attached to the region where the semiconductor wafer is attached, and the kerf width can be expanded more favorably, thereby improving pick-up property.

Here, "outer circumference" means a peripheral area of a semiconductor wafer.

That is, the composite sheet for forming a protective film of the present invention has good pick-up suitability, for example, the target semiconductor wafer can be picked up with high selectivity. In addition, cracking and defect of the semiconductor wafer are suppressed at this time.

Further, in the composite sheet for forming a protective film of the present invention, the film for forming a protective film is energy ray-curable, and the composite sheet for forming a protective film before the film for forming a film having a thermosetting protective film is used. In this case, the protective film can be formed by hardening for a short time.

The adhesive force between the support sheet in the laminate and the film for forming a protective film is preferably 100 mN/25 mm or more, more preferably 150 mN/25 mm or more, still more preferably 220 mN/25 mm or more, and further preferably 10000 mN/ 25 mm or less, more preferably 8000 mN/25 mm or less, and particularly preferably 7000 mN/25 mm or less. By adjusting to the lower limit or more, the scattering of the germanium wafer during the dicing is suppressed, and the intrusion of the cutting water into the film for forming the protective film and the support sheet can be prevented. In addition, by adjusting to the upper limit or less, it is possible to easily adjust the adhesion between the protective film and the support sheet when the protective film is subsequently cured by irradiation with an energy ray.

In other words, the adhesion between the support sheet in the laminate and the film for forming a protective film is preferably from 100 mN/25 mm to 10000 mN/25 mm, more preferably from 150 mN/25 mm to 8000 mN/25 mm. Good for 220mN/25mm to 7000mN/25mm or less.

The film for forming a protective film is cured by irradiation with an energy ray to form a protective film. The protective film protects the back surface of the semiconductor wafer or the semiconductor wafer (the surface opposite to the electrode forming surface). The film for forming a protective film is soft and can be easily attached to an attached object. Further, when the protective film forming film is irradiated with an energy ray to form a protective film, the adhesive force between the protective film and the support sheet is preferably 50 mN/25 mm to 1500 mN/25 mm, more preferably 52 mN/25 mm to 1450 mN/ 25mm, especially preferably 53mN/25mm to 1430mN/25mm. When the adhesion force is equal to or higher than the lower limit value and the semiconductor wafer with the protective film is picked up, the pickup of the semiconductor wafer with the protective film outside the target is suppressed, and the selectivity is high. A semiconductor wafer with a protective film attached to the target is picked up. In addition, when the semiconductor wafer with the protective film is picked up by the adhesion force being equal to or less than the above upper limit value, cracking and defect of the semiconductor wafer are suppressed. As described above, the composite sheet for forming a protective film has a good pick-up property by the aforementioned adhesive force within a specific range.

Further, in the composite sheet for forming a protective film of the present invention, the film for forming a protective film is energy ray-curable, and is composited with the prior protective film for forming a film for forming a protective film having thermosetting properties. In the case of a sheet, a protective film can be formed by hardening in a short time.

The thickness of the semiconductor wafer or the semiconductor wafer to be used as the composite sheet for forming a protective film of the present invention is not particularly limited, and from the viewpoint of obtaining more remarkable effects of the present invention, it is preferably from 30 μm to 1000 μm, more preferably 100 μm. Up to 300 μm.

In the present specification, the term "thickness" means an average value obtained by measuring the thickness by a contact thickness gauge at any five locations.

Hereinafter, the configuration of the present invention will be described in detail.

◎Support film

The support sheet has a light shielding layer in a region in the vicinity of the peripheral portion. Here, the term "light-shielding layer" refers to a layer that shields the energy ray when the energy-curable protective film-forming film is irradiated with an energy ray to cure the film for forming a protective film. The light-shielding layer is not limited as long as it has a function of shielding energy rays such as ultraviolet rays, X-rays, and electron beams that cure the film for forming a protective film. The full-shielding energy ray, in particular, a layer through which the energy ray-activated energy source activated by the photo-polymerization initiator in the energy-curable protective film forming film is transmitted, preferably has a transmittance of 50% or less. The layer is more preferably a layer having a transmittance of the energy ray of 10% or less.

That is, as one aspect, the light shielding layer means a layer having a transmittance of an energy ray of 50% or less, preferably 10% or less, and particularly preferably 0%.

As the light shielding layer, it is preferable that the inner side is hollowed out into a circular shape in accordance with the size of the semiconductor wafer. The diameter (diameter) of the hollowed out circular shape is preferably 95% to 140%, more preferably 98% to 135%, and even more preferably 100% to 130% of the outer diameter of the semiconductor wafer. The shape of the light shielding layer may be a ring shape. The light-shielding layer is a layer located in a region in the vicinity of the peripheral portion of the support sheet, and shields the region near the peripheral portion of the film for forming a protective film when the energy-sensitive film is applied to the film for forming a protective film. An energy ray is irradiated to a portion of the adhesion region of the semiconductor wafer in the film for formation. When the inner side of the light-shielding layer has a circular shape, the diameter of the hollowed-out circular shape is set to 95% or more of the outer diameter of the semiconductor wafer because there is a possibility that even the outer periphery of the semiconductor wafer is present. It is slightly shielded by the light shielding layer, and it is only impossible to pick up an unnecessary wafer (ie, a triangular wafer) at the end of the semiconductor wafer without causing a problem.

As a material having a function of shielding the aforementioned energy rays, it is preferably selected in accordance with the kind of the photopolymerization initiator. Specifically, the material having a function of shielding the energy ray is not particularly limited, and examples thereof include ultraviolet absorbing properties such as CeO ₂ , TiO ₂ , ZnO, Fe ₂ O ₃ , V ₂ O ₅ , and PbO. Inorganic ink (ink), or aluminum vapor-deposited PET (polyethylene terephthalate (polyethylene terephthalate) film (aluminum vapor-deposited polyethylene terephthalate film).

The light shielding layer may be composed of a printed layer. The printing method is not particularly limited, and examples thereof include a relief printing method, a lithographic printing method, a gravure printing method, and a stencil printing method. The thickness of the printed layer is not particularly limited, but is usually 50 μm or less, and may be 0.05 μm to 50 μm, preferably 0.05 μm to 10 μm, and more preferably 0.1 μm to 2 μm.

In other words, as an aspect of the printing layer, an ink containing an ultraviolet absorbing inorganic substance such as CeO ₂ , TiO ₂ , ZnO, Fe ₂ O ₃ , V ₂ O ₅ , or PbO may be used. The layer formed.

In the case of the protective film forming film, the protective film forming film is observed from the upper side when the semiconductor film is attached to the protective film forming film. An area in the support sheet in which the semiconductor wafer is not attached to the periphery (surrounding) of the semiconductor wafer and the area where the energy line is shielded and not hardened.

In another aspect, the “region in the vicinity of the peripheral portion of the support sheet” means a region corresponding to the shape of the semiconductor wafer in the support sheet when the semiconductor wafer is attached to the film for forming a protective film ( For example, a region other than the circular region corresponding to the size of the aforementioned semiconductor wafer.

Further, the "outer diameter" is defined as the maximum value of the distance between two parallel lines that are tangent to the outer side of the object. That is, the so-called "semiconductor wafer "Outer diameter" means the maximum value of the distance between two parallel lines that place a semiconductor wafer on a plane and is tangent to the upper surface of the aforementioned semiconductor wafer. The outer diameter of the semiconductor wafer can be measured using a vernier caliper or the like.

In the present invention, the "region in the vicinity of the peripheral portion of the film for forming a protective film" means the outer periphery of the semiconductor wafer in the film for forming a protective film when the semiconductor wafer is attached to the film for forming a protective film. The area where the semiconductor wafer is not attached.

The support sheet may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. In the case where the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

Furthermore, in the present specification, the present invention is not limited to the case of the support sheet, and the phrase "the plural layers may be the same or different from each other" means that "all layers may be the same, or all layers may be different, and only a part of the layers may be the same", and The phrase "the plural layers are different from each other" means that "at least one of the constituent materials and the thickness of each layer is different from each other".

Preferred examples of the support sheet include a support sheet in which an adhesive layer is laminated on a substrate in a direct contact manner, and a support sheet formed by laminating an adhesive layer on the substrate. Support sheets for materials.

Hereinafter, according to each type of the above-mentioned support sheet, the description will be described with reference to the drawings. An example of the composite sheet for forming a protective film of the invention. In addition, in the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, it is convenient to see a part that is a main part in an enlarged manner, and the size ratio of each component is not limited to the actual one.

Fig. 1 is a cross-sectional view showing an embodiment of a composite sheet for forming a protective film of the present invention in a schematic manner.

Fig. 2 is a view showing the back surface of the composite sheet for forming a protective film of Fig. 1.

The composite sheet 1A for forming a protective film has a configuration in which a protective film is formed on one surface 10a of the support sheet 10 which is a laminate of the substrate 11, the adhesive layer 12, and the light shielding layer 24. Membrane 13.

Specifically, in the composite sheet 1A for forming a protective film, the adhesive layer 12 is provided on the substrate 11, and the protective film forming film 13 is provided on the adhesive layer 12, and the substrate 11 is provided on the lower portion of the substrate 11 (that is, the substrate 11). The region in the vicinity of the peripheral portion of the support sheet 10 and the light shielding layer 24 formed of an annular printed layer are provided on the surface on the opposite side to the side on which the adhesive layer 12 is provided. In addition, the protective film forming composite sheet 1A further includes a release film 15 on the protective film forming film 13.

In the composite sheet for forming a protective film of Figs. 1 and 2, the lower portion of the substrate 11 (i.e., the surface of the substrate 11B opposite to the side having the adhesive layer 12) is printed by a ring shape. The light shielding layer 24 is formed of a layer, but the light shielding layer 24 may be provided between the substrate 11 and the adhesive layer 12, or may be provided in a ring shape between the adhesive layer 12 and the film 13 for forming a protective film.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, on the surface 12a of the adhesive layer 12 (that is, in the adhesive layer 12 and in contact with the substrate 11). The film 13 for forming a protective film is formed on the surface 13a of the film 13 for forming a protective film, that is, the surface of the film 13 for forming a protective film, which is in contact with the adhesive layer 12, in the entire area of the surface of the protective film forming film 13. The adhesive adhesive layer 16 is laminated in a region in the vicinity of the peripheral portion of the protective film forming film 13 in the vicinity of the peripheral surface of the protective film forming film 13 , and the adhesive for the jig is not laminated on the surface 13 a of the protective film forming film 13 . The surface of the layer 16 and the surface 16a of the adhesive layer 16 for the jig (the upper surface, that is, the surface on the side opposite to the surface in contact with the film 13 for forming a protective film in the adhesive layer 16 for the jig, and the jig for the jig Next, the side surface of the agent layer 16 is laminated with a release film 15.

In the composite sheet 1A for forming a protective film, the adhesion between the cured protective film forming film 13 (i.e., the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is preferably 50mN/25mm to 1500mN/25mm.

The adhesive-use adhesive layer 16 may be, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure in which a double-layered layer of a core material has a layer containing an adhesive component.

The composite sheet 1A for forming a protective film shown in Fig. 1 is used in the following manner: in the state where the release film 15 is removed, the sheet of the protective film formation film 13 is used. The back surface of the semiconductor wafer (not shown) is attached to the surface 13a, and the upper surface of the surface 16a of the adhesive adhesive layer 16 is attached to a jig such as a ring frame.

Fig. 3 is a cross-sectional view showing another embodiment of the composite sheet for forming a protective film of the present invention in a schematic manner. In the drawings, the same components as those in the above-described drawings are denoted by the same reference numerals, and the detailed description of the symbols will be omitted.

The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for protective film formation shown in FIGS. 1 and 2 except that the adhesive layer 16 for a jig is not provided. In other words, the protective film-forming composite sheet 1B has a structure in which a protective film-forming film 13 is laminated on one surface 10a of the support sheet 10 which is a laminate of the substrate 11, the adhesive layer 12, and the light-shielding layer 24. .

Specifically, in the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11 on the surface 12a of the adhesive layer 12 (that is, the conjugated layer in the adhesive layer 12). The protective film forming film 13 is formed over the entire area of the substrate 11 in the entire area of the surface on which the material 11 is in contact with the surface of the substrate 11 (that is, the side of the substrate 11 opposite to the side having the adhesive layer 12). In the surface of the protective sheet 10, a light-shielding layer 24 composed of a ring-shaped printed layer is laminated, and a peeling film 15 is formed over the entire surface 13a of the surface 13a of the protective film forming film 13.

The composite sheet 1B for forming a protective film shown in Fig. 3 is used in the following manner. In the state in which the peeling film 15 is removed, the back surface of the semiconductor wafer (not shown) is attached to a part of the center side of the surface 13a of the film 13 for forming a protective film, and the film for protective film formation 13 is attached. The area near the peripheral portion is attached to a jig such as a ring frame.

Fig. 4 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for protective film formation shown in FIGS. 1 and 2 except that the adhesive layer 12 is not provided. In other words, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed only of the base material 11 and the light shielding layer 24.

In addition, a film 13 for forming a protective film is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and is formed on the lower portion of the substrate 11 (that is, the substrate 11 is provided with a protective film). The surface on the opposite side of the film 13 is a region in the vicinity of the peripheral portion of the support sheet 10, and a light-shielding layer 24 composed of an annular printed layer is laminated; and the surface 13a of the film 13 for protective film formation is further laminated. (a portion of the protective film forming film 13 on the side opposite to the side including the substrate 11), that is, a region in the vicinity of the peripheral portion of the protective film forming film 13 is laminated with the adhesive layer 16 for the jig. In the surface 13a of the film 13 for forming a protective film, the surface of the adhesive layer 16 for the fixture and the surface 16a of the adhesive layer 16 for the jig are not laminated (the upper surface, that is, the adhesive layer 16 for the jig) The release film 15 is laminated on the surface on the opposite side to the surface on which the film for protective film formation 13 is contacted and the side surface in the adhesive layer 16 for the jig.

In the composite sheet 1C for forming a protective film, the adhesion between the film 13 for protective film formation (that is, the protective film) and the support sheet 10 after curing, in other words, the adhesion between the protective film and the substrate 11 is preferably 50 mN. /25mm to 1500mN/25mm.

The composite sheet 1C for forming a protective film shown in Fig. 4 is used in the form of a film for forming a protective film in a state in which the release film 15 is removed, similarly to the composite sheet 1A for protective film formation shown in Fig. 1 . The back surface of the semiconductor wafer (not shown) is attached to the surface 13a of the 13 and the upper surface of the surface 16a of the adhesive adhesive layer 16 is attached to a jig such as a ring frame.

Fig. 5 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for protective film formation shown in FIG. 4 except that the adhesive layer 16 for a jig is not provided. In the composite sheet 1D for forming a protective film, the protective film forming film 13 is laminated on one surface 11a of the substrate 11, and is formed on the lower portion of the substrate 11 (that is, the protective film is formed on the substrate 11). The surface in the vicinity of the peripheral portion of the support sheet 10 is provided with a light-shielding layer 24 composed of a ring-shaped printing layer on the surface 13a of the film 13 for protective film formation (that is, A release film 15 is provided over the entire area of the protective film forming film 13 on the side opposite to the side on which the substrate 11 is provided.

The composite sheet 1D for forming a protective film shown in Fig. 5 is made in the following manner In the same manner as the composite sheet 1B for protective film formation shown in FIG. 3, a semiconductor wafer is attached to a part of the center side of the surface 13a of the film 13 for forming a protective film in a state where the release film 15 is removed. The back surface (not shown) is attached to a jig such as a ring frame by a region in the vicinity of the peripheral edge portion of the film 13 for forming a protective film.

Fig. 6 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1E for forming a protective film shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 1 except that the shape of the film for forming a protective film is different. In other words, the protective film-forming composite sheet 1E has a structure in which a protective film forming film 23 is laminated on one surface 10a of the support sheet 10 which is a laminate of the substrate 11 and the adhesive layer 12 and the light-shielding layer 24.

Specifically, in the composite sheet 1E for forming a protective film, the adhesive layer 12 is provided on the substrate 11, and the protective film forming film 23 is provided on the adhesive layer 12 at the lower portion of the substrate 11 (that is, the substrate). A region in the vicinity of the peripheral edge portion of the support sheet 10 in the region of 11 on the side opposite to the side on which the adhesive layer 12 is provided includes a light shielding layer 24 composed of an annular printed layer. Further, in the composite sheet 1E for forming a protective film, the release film 15 is further provided on the film 23 for forming a protective film.

In the composite sheet 1E for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, on the surface 12a of the adhesive layer 12 (that is, sticky A film for forming a protective film 23 is laminated on a portion of the center side of the surface 12a which is a part of the surface of the primer layer 12 on the side opposite to the side on which the substrate 11 is provided. Further, the surface of the protective film forming film 23 and the surface 23a of the protective film forming film 23 are not laminated on the surface 12a of the adhesive layer 12 (the upper surface, that is, the adhesive and adhesive layer 12 in the protective film forming film 23). The release film 15 is laminated on the surface on the opposite side and the side surface of the film 23 for forming a protective film.

When the protective film forming composite sheet 1E is viewed from above, the surface area of the protective film forming film 23 is smaller than the adhesive layer 12, and has a circular shape or the like, for example.

In the composite sheet 1E for forming a protective film, the adhesion between the cured protective film forming film 23 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is preferably 50mN/25mm to 1500mN/25mm.

The composite sheet 1E for forming a protective film shown in Fig. 6 is used in a state in which a back surface of a semiconductor wafer (not shown) is attached to the surface 23a of the film 23 for forming a protective film in a state where the release film 15 is removed. The surface of the surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame.

Further, in the composite sheet 1E for forming a protective film shown in FIG. 6, the surface of the protective film forming film 23 is not laminated on the surface 12a of the adhesive layer 12, and An adhesive layer (not shown) for the jig is laminated in the same manner as shown in Figs. 1 and 4 . The composite sheet 1E for protective film formation having such an adhesive layer for a jig is used in the following manner: similarly to the composite sheet for forming a protective film shown in Figs. 1 and 4, the surface of the adhesive layer for a jig is used. Attached to a fixture such as a ring frame.

In the composite sheet for forming a protective film of the present invention, the adhesive sheet for a jig can be provided regardless of the form of the support sheet and the film for forming a protective film. However, as shown in FIG. 1 and FIG. 4, the composite sheet for forming a protective film of the present invention having the adhesive layer for a jig is preferably provided with an adhesive layer for a protective film on the film for forming a protective film.

The composite sheet for forming a protective film of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. 1 to 6, and may be modified or deleted as shown in FIGS. 1 to 6 within the scope of the effect of the present invention. The composite film for forming a protective film is partially formed, or another structure is added to the composite sheet for forming a protective film described above.

For example, in the composite sheet for forming a protective film shown in FIG. 4 and FIG. 5, an intermediate layer may be provided between the substrate 11 and the film 13 for forming a protective film. As the intermediate layer, any intermediate layer can be selected depending on the purpose.

Further, in the composite sheet for forming a protective film shown in FIG. 1, FIG. 3, and FIG. 6, an intermediate layer may be provided between the substrate 11 and the adhesive layer 12. In other words, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by sequentially laminating a substrate, an intermediate layer, and an adhesive layer. Here, the so-called intermediate layer and diagram 4 and the intermediate layer which can be provided in the composite sheet for forming a protective film shown in Fig. 5 is the same.

Further, in the composite sheet for forming a protective film shown in FIG. 1 to FIG. 6, a layer other than the intermediate layer may be provided at an arbitrary position.

Further, in the composite sheet for forming a protective film of the present invention, a part of the gap may be formed between the release film and the layer directly in contact with the release film.

Further, in the composite sheet for forming a protective film of the present invention, the size or shape of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, it is preferable that the layer directly contacting the film for forming a protective film in the support sheet such as the adhesive layer is non-energy line curable. Such a composite sheet for forming a protective film can more easily pick up a semiconductor wafer having a protective film on its back surface.

The support sheet can be transparent or opaque, and can be colored according to the purpose.

In the invention in which the film for forming a protective film has energy ray curability, the support sheet is preferably a support sheet through which energy rays are transmitted.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in such a range and the energy ray (ultraviolet rays) is applied to the film for forming a protective film via the support sheet, the degree of hardening of the film for forming a protective film is further improved.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited, and may be, for example, 95%.

That is, as a mode, the transmittance of light having a wavelength of 375 nm in the support sheet is preferably from 30% to 95%, more preferably from 50% to 95%, particularly preferably from 70% to 95%.

Further, in the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.

When the transmittance of the light is in such a range, the protective film forming film or the protective film is irradiated with the laser light through the support sheet, and when printing is performed, the printing can be performed more clearly.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited, and may be, for example, 95%.

That is, as a mode, the transmittance of light having a wavelength of 532 nm in the support sheet is preferably from 30% to 95%, more preferably from 50% to 95%, particularly preferably from 70% to 95%.

Further, in the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in such a range, the protective film forming film or the protective film is irradiated with the laser light through the support sheet, and when printing is performed, the printing can be performed more clearly.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited, and may be, for example, 95%.

That is, as a mode, the transmittance of light having a wavelength of 1064 nm in the support sheet is preferably from 30% to 95%, more preferably from 50% to 95%, particularly preferably from 70% to 95%.

Next, each layer constituting the support sheet will be described in more detail.

○Substrate

The base material is in the form of a sheet or a film, and examples of the constituent material of the substrate include various resins.

Examples of the resin include low density polyethylene (abbreviated as LDPE; low density polyethylene), linear low density polyethylene (abbreviated as LLDPE; linear low density polyethylene), and high density polyethylene (referred to as HDPE; high density). Polyethylene; polyethylene other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid Vinyl copolymers such as copolymers, ethylene-(meth)acrylate copolymers and ethylene-bornene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chlorides such as polyvinyl chloride and vinyl chloride copolymers Resin (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly a polyester such as ethylene phthalate or polyethylene-2,6-naphthalenedicarboxylate; a polyester such as a wholly aromatic polyester having an aromatic ring group; and a copolymer of two or more of the foregoing polyesters; Poly(meth)acrylate; polyamine Acid ester; polyacrylic acid urethane; polyimine; polyamine; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; Polyether ketone and the like.

In addition, as the resin, for example, a polymer alloy such as a mixture of the polyester and a resin other than the polyester may be used. The polymer alloy of the polyester and the resin other than the polyester is preferably a relatively small amount of the resin other than the polyester.

In addition, as the resin, for example, one or two or more kinds of the above-exemplified resins may be used as a cross-linking resin, and one or two or more kinds of ionic polymerizations of the above-exemplified resins may be used. Remodeling resin such as matter.

Further, in the present specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same is true for terms similar to (meth)acrylic acid.

The resin constituting the substrate may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

The base material may be composed of one layer (single layer) or a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different, and the combination of the plurality of layers is not particularly limited.

The thickness of the substrate is preferably from 50 μm to 300 μm, more preferably from 60 μm to 100 μm. By the thickness of the substrate being such a range, the flexibility of the composite sheet for forming a protective film, and the adhesion to a semiconductor wafer or a semiconductor wafer The appendage is further improved.

Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.

The substrate preferably has a high thickness precision, that is, any portion can suppress thickness unevenness. Among the above-mentioned constituent materials, examples of the material which can be used to constitute such a substrate having high thickness precision include polyolefin, polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymerization. Things and so on.

The base material may contain various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the above resin.

The optical characteristics of the substrate may satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent or opaque, may be colored according to the purpose, or may be vapor-deposited.

Further, in the invention in which the film for forming a protective film has energy ray curability, the substrate is preferably a substrate through which energy rays are transmitted.

The surface of the substrate may be subjected to the following treatment to improve adhesion to other layers such as an adhesive layer provided on the substrate: by embossing treatment such as blasting or solvent treatment; or corona discharge treatment or electron beam treatment Irradiation Treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.

Alternatively, the surface of the substrate may be subjected to a primer treatment.

Further, the substrate may have an antistatic coating layer or a layer for the following use. When the composite sheet for forming a protective film is stacked and stored, the substrate is prevented from adhering to the other sheet or substrate to the adsorption stage.

Among these, the substrate is preferably subjected to electron beam irradiation treatment in terms of suppressing the occurrence of fragmentation of the substrate due to blade rubbing during cutting.

The substrate can be produced by a known method. For example, the resin-containing substrate can be produced by molding a resin composition containing the above resin.

○Adhesive layer

The adhesive layer is in the form of a sheet or a film and contains an adhesive.

Examples of the pressure-sensitive adhesive include adhesion of an acrylic resin, an urethane resin, a rubber resin, a polyoxyn resin, an epoxy resin, a polyvinyl ether, a polycarbonate, and an ester resin. The resin is preferably an acrylic resin.

In addition, in the present specification, the term "adhesive resin" includes both an adhesive resin and a resin having adhesive properties, and for example, not only a resin having adhesiveness but also an additive and the like. A resin which exhibits adhesion or a resin which exhibits adhesion by a triggering agent such as heat or water is used in combination.

The adhesive layer may be composed of one layer (single layer) or two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different, and the combination of the plurality of layers is not particularly limited. .

The thickness of the adhesive layer is preferably from 1 μm to 100 μm, more preferably from 1 μm to 60 μm, still more preferably from 1 μm to 30 μm.

Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.

The optical properties of the adhesive layer can satisfy the optical characteristics of the support sheet described above. That is, the adhesive layer may be transparent or opaque, and may be colored according to the purpose.

Further, in the invention in which the film for forming a protective film has energy ray curability, the pressure-sensitive adhesive layer is preferably an adhesive layer through which energy rays pass.

The adhesive layer can be formed using an energy ray-curable adhesive, or can be formed using a non-energetic curable adhesive. The adhesive layer formed by the energy ray-curable adhesive can easily adjust the physical properties before and after hardening.

<<Adhesive composition>>

The adhesive layer may be formed of an adhesive composition containing an adhesive. For example, an adhesive composition is applied to the surface of the target layer of the adhesive layer, and the adhesive composition is dried as needed, whereby an adhesive layer can be formed at the target portion. A more specific method of forming the adhesive layer will be described in detail later together with the formation method of the other layers. The content ratio of the components which are not vaporized at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. In the present specification, the term "normal temperature" means a temperature which is not particularly cold or particularly hot, that is, a normal temperature, and examples thereof include a temperature of 15 ° C to 25 ° C.

The adhesive composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater, knife coater, bar coater, gravure coater, and roll coater. Cloth machine, roll coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, contact coater Wait.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent to be described later, it is preferably dried by heating; in this case, it is preferably, for example, 70 ° C to 130 ° C and 10 seconds to 5 seconds. Dry under minute conditions.

When the adhesive layer is energy sclerosing, the adhesive composition containing the energy ray-curable adhesive, that is, the energy ray hardening viscosity The adhesive composition is, for example, the following adhesive composition: the adhesive composition (I-1), and the non-energy-curable adhesive resin (I-1a) (hereinafter, simply referred to as "adhesiveness" Resin (I-1a)") and an energy ray-curable compound; an adhesive composition (I-2) containing an energy ray-curable adhesive resin (I-2a) (hereinafter sometimes referred to simply as "adhesiveness") Resin (I-2a)"), the adhesive resin (I-2a) is introduced with an unsaturated group in the side chain of the non-energy-curable adhesive resin (I-1a); the adhesive composition (I-3) The adhesive resin (I-2a) and the energy ray-curable compound are contained.

<Adhesive Composition (I-1)>

As described above, the pressure-sensitive adhesive composition (I-1) contains a non-energy-curable adhesive resin (I-1a) and an energy ray-curable compound.

[Adhesive resin (I-1a)]

The adhesive resin (I-1a) is preferably an acrylic resin.

The acrylic resin may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

The structural unit of the acrylic resin may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the present specification, "derived from" means that the chemical structure changes to carry out polymerization.

As the alkyl (meth)acrylate, for example, an alkane is exemplified The alkyl group of the base ester has an alkyl group having 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched.

Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (A) Ethyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (meth)acrylic acid) Lauryl ester), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, Cetyl (meth) acrylate (also known as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (A) (poly) stearyl acrylate), (meth) acrylate Nine alkyl ester, (meth) acrylate, eicosyl acrylate.

The acrylic polymer is preferably a structural unit having an alkyl (meth)acrylate having a carbon number of 4 or more derived from the alkyl group, in terms of improving the adhesion of the adhesive layer. Further, the alkyl group preferably has a carbon number of 4 to 12, more preferably 4 to 8, in terms of further improving the adhesion of the adhesive layer. Further, the alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group is preferably an alkyl acrylate.

In the acrylic polymer, it is preferred to further have a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate.

Examples of the functional group-containing monomer include a monomer which can be reacted with a crosslinking agent to be described later to form a starting point for crosslinking, or a functional group and an unsaturated group to be described later. The unsaturated group in the compound reacts, and an unsaturated group is introduced into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.

That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylate; vinyl alcohol, A non-(meth)acrylic unsaturated alcohol such as allyl alcohol (that is, an unsaturated alcohol having no (meth)acryl fluorenyl skeleton).

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid such as (meth)acrylic acid or crotonic acid (that is, a monocarboxylic acid having an ethylenically unsaturated bond); fumaric acid; An ethylenically unsaturated dicarboxylic acid such as itaconic acid, maleic acid or citraconic acid (that is, a dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the above ethylenically unsaturated dicarboxylic acid; A carboxyalkyl (meth)acrylate such as 2-carboxyethyl acrylate.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, more preferably a hydroxyl group-containing monomer.

The functional group-containing monomer constituting the acrylic polymer may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably from 1% by mass to 35% by mass, more preferably 2%, based on the total mass of the structural unit constituting the acrylic polymer. The mass% to 32% by mass, particularly preferably 3% by mass to 30% by mass.

In addition to the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the functional group-containing monomer, the acrylic polymer may further have a structural unit derived from another monomer.

The other monomer is not particularly limited as long as it is a monomer copolymerizable with an alkyl (meth)acrylate or the like.

Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

The other monomer constituting the acrylic polymer may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

The acrylic polymer can be used as the above non-energy-curable adhesive resin (I-1a).

On the other hand, a compound obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (also referred to as an energy ray polymerizable group) can be used as the above. Energy line hardenable adhesive resin (I-2a).

In the present specification, the term "energy ray polymerizability" means a property of polymerization by irradiation of an energy ray.

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

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

[Energy curing compound]

The energy ray-curable compound contained in the adhesive composition (I-1) includes a monomer or oligomer which has an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray.

In the energy ray-curable compound, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol VI (A). Poly(meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; amine (meth)acrylate Ester; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate, and the like.

In the energy ray-curable compound, examples of the oligomer include an oligomer obtained by polymerizing the above-exemplified monomers.

The energy ray-curable compound is preferably a (meth)acrylic acid urethane or a (meth)acrylic acid urethane in terms of a relatively large molecular weight and a tendency to lower the storage modulus of the adhesive layer. Oligomer.

The energy ray-curable compound to be contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the above adhesive composition (I-1), the aforementioned energy ray-curable compound The content is preferably from 1% by mass to 95% by mass, more preferably from 5% by mass to 90% by mass, even more preferably from 10% by mass to 85% by mass, based on the total mass of the aforementioned adhesive composition (I-1). .

[crosslinking agent]

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

The crosslinking agent reacts with the aforementioned functional group to crosslink the adhesive resin (I-1a) with each other.

Examples of the crosslinking agent include isocyanate crosslinking agents such as toluene diisocyanate, hexamethylene diisocyanate, benzodimethyl diisocyanate, and an adduct of these diisocyanates (that is, crosslinking having an isocyanate group). Epoxy crosslinking agent such as ethylene glycol glycidyl ether (that is, a crosslinking agent having a glycidyl group); hexa[1-(2-methyl)-aziridine]triphosphine triazine An aziridine-based crosslinking agent (that is, a crosslinking agent having an aziridine group); a metal chelate-based crosslinking agent such as an aluminum chelate compound (that is, a crosslinking agent having a metal chelate structure) An isocyanurate-based crosslinking agent (that is, a crosslinking agent having an isocyanuric acid skeleton) or the like.

The crosslinking agent is preferably an isocyanate crosslinking agent in terms of improving the cohesive force of the adhesive, improving the adhesion of the adhesive layer, and facilitating the acquisition.

The amount of the crosslinking agent contained in the adhesive composition (I-1) may be one or two or more. When two or more types are used, these combinations and ratios may be arbitrarily selected.

In the above-mentioned adhesive composition (I-1), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass, per 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferably from 0.3 part by mass to 15 parts by mass to 20 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator is sufficiently subjected to a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. a ketone compound; a fluorenylphosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide; a thiol compound such as a phenyl sulfide or a tetramethyl thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; Titanocene compound such as titanium; thioxanthone compound such as thioxanthone; peroxide compound; diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; benzophenone; 2,4-diethyl Thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroindole and the like.

In addition, as the photopolymerization initiator, for example, a ruthenium compound such as 1-chloroindole or a photo sensitizer such as an amine can be used.

The photopolymerization initiator contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass, per 100 parts by mass of the content of the energy ray-curable compound. 10 parts by mass, particularly preferably from 0.05 parts by mass to 5 parts by mass.

[Other additives]

In the adhesive composition (I-1), other additives not belonging to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include an antistatic agent, an antioxidant, a softener (plasticizer), a filler (filler), a rust preventive, a colorant (pigment, dye), a sensitizer, and an adhesion-imparting agent. A known additive such as a reaction retarder or a crosslinking accelerator (catalyst).

Further, the reaction retardant is, for example, inhibited from being mixed into the adhesive group. The action of the catalyst in the product (I-1) causes the cross-linking reaction outside the target in the adhesive composition (I-1) in storage. The reaction retardation agent is, for example, a compound which forms a chelate complex by a chelate compound, and more specifically, has two or more carbonyl groups (-C (in one molecule). Compound of =O)-).

The other additives contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-1), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-1) may also contain a solvent. The adhesive composition (I-1) has an applicability to the coating target surface by containing a solvent.

The solvent is preferably an organic solvent, and examples of the organic solvent include a ketone such as methyl ethyl ketone or acetone; an ester such as ethyl acetate (for example, a carboxylic acid ester); and an ether such as tetrahydrofuran or dioxane. An aliphatic hydrocarbon such as cyclohexane or n-hexane; an aromatic hydrocarbon such as toluene or xylene; an alcohol such as 1-propanol or 2-propanol; and the like.

As the solvent, for example, when the adhesive resin (I-1a) is produced, The solvent to be used is not directly removed from the adhesive resin (I-1a) but used directly in the adhesive composition (I-1), and may be additionally added and manufactured for adhesion when the adhesive composition (I-1) is produced. The solvent used in the resin (I-1a) is the same type or a different type of solvent.

The solvent contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-1), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive Composition (I-2)>

As described above, the adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) which is a non-energy-curable adhesive resin (I). The side chain of -1a) is introduced with an unsaturated group.

[Adhesive resin (I-2a)]

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

The unsaturated group-containing compound further has, in addition to the energy ray polymerizable unsaturated group, a group having a bond The functional group in the resin (I-1a) reacts to bond with the adhesive resin (I-1a).

Examples of the energy ray polymerizable unsaturated group include a (meth)acryl fluorenyl group, a vinyl group (also referred to as a secondary ethyl group), an allyl group (also referred to as a 2-propenyl group), and the like. (Methyl) acrylonitrile.

The group which can be bonded to the functional group in the adhesive resin (I-1a) may, for example, be an isocyanate group and a glycidyl group which may be bonded to a hydroxyl group or an amine group, and may be bonded to a carboxyl group or an epoxy group. Hydroxyl groups and amine groups.

Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl decyl isocyanate, and glycidyl (meth)acrylate.

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

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

[crosslinking agent]

For example, the same acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive in the adhesive resin (I-1a). In the case of the resin (I-2a), the adhesive composition (I-2) may further contain a crosslinking agent.

The crosslinking agent in the adhesive composition (I-2) is the same as the crosslinking agent in the adhesive composition (I-1).

The amount of the crosslinking agent contained in the adhesive composition (I-2) may be one or two or more. When two or more kinds are used, these combinations and ratios may be arbitrarily selected.

In the above-mentioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 part by mass, per 100 parts by mass of the content of the adhesive resin (I-2a). It is especially preferably from 0.3 part by mass to 15 parts by mass to 20 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator is sufficiently subjected to a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-2) is the same as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass, based on 100 parts by mass of the content of the adhesive resin (I-2a). The portion is preferably 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

In the adhesive composition (I-2), other additives not belonging to any of the above components may be contained within the range which does not impair the effects of the present invention.

The other additives mentioned above in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, these combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-2), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-2) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent mentioned in the adhesive composition (I-2) is the same solvent as the solvent in the adhesive composition (I-1).

The adhesive composition (I-2) may contain only one solvent or may be Two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive Composition (I-3)>

As described above, the pressure-sensitive adhesive composition (I-3) contains the above-mentioned adhesive resin (I-2a) and an energy ray-curable compound.

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

[Energy curing compound]

The energy ray-curable compound to be contained in the adhesive composition (I-3) includes a monomer and an oligomer which have an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray, and examples thereof include The same compound as the energy ray-curable compound contained in the adhesive composition (I-1).

The energy ray-curable compound to be contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

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

[Photopolymerization initiator]

The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator is sufficiently subjected to a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-3) is the same as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 parts by mass to 100 parts by mass based on 100 parts by mass of the total of the adhesive resin (I-2a) and the energy ray-curable compound. The parts by mass are more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

In the adhesive composition (I-3), other additives not belonging to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include an adhesive composition (I-1). Other additives in the same compound.

The other additives contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-3), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-3) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent in the adhesive composition (I-3) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3)>

The adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) are mainly described above, but all the adhesives other than these three adhesive compositions are described. Composition (in this specification, it is called "adhesive" The component (I-1) to the adhesive composition other than the adhesive composition (I-3) can be similarly used as the component described as the component.

As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy ray-curable adhesive composition, a non-energy curing adhesive may be cited. Composition.

Examples of the non-energy-curable adhesive composition include an acrylic resin, an urethane resin, a rubber resin, a polyoxyn resin, an epoxy resin, a polyvinyl ether, and a polycarbonate. The adhesive composition (I-4) of the non-energy-curable adhesive resin (I-1a) such as an ester or an ester resin is preferably an adhesive composition containing an acrylic resin.

The adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contains one or more kinds of crosslinking agents, and the content of the crosslinking agent can be set to The above adhesive composition (I-1) and the like are the same.

<Adhesive Composition (I-4)>

The preferred adhesive composition (I-4) is, for example, an adhesive composition containing the above-mentioned adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a) in the adhesive composition (I-4)]

The adhesive resin (I-1a) in the adhesive composition (I-4) is the same as the adhesive resin (I-1a) in the adhesive composition (I-1).

The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

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

[crosslinking agent]

In the case where the above-mentioned acrylic polymer having a structural unit derived from a functional group-containing monomer is further used as the above-mentioned adhesive resin (I-1a), in addition to the structural unit derived from the alkyl (meth)acrylate The adhesive composition (I-4) preferably further contains a crosslinking agent.

The crosslinking agent in the adhesive composition (I-4) is the same as the crosslinking agent in the adhesive composition (I-1).

The amount of the crosslinking agent contained in the adhesive composition (I-4) may be one or two or more. When two or more kinds are used, these combinations and ratios may be arbitrarily selected.

In the above-mentioned adhesive composition (I-4), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass, per 100 parts by mass of the content of the adhesive resin (I-1a). Up to 20 parts by mass, particularly preferably 0.3 parts by mass to 15 parts by mass.

[Other additives]

In the adhesive composition (I-4), other additives not belonging to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-4), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-4) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent in the adhesive composition (I-4) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be appropriately adjusted.

In the composite sheet for forming a protective film of the present invention, the adhesive layer is preferably non-energy line curable. The reason is that if the adhesive layer is energy ray-curable, there is a case where the adhesive layer cannot be simultaneously cured when the film for forming a protective film is cured by irradiation of the energy ray. When the adhesive layer and the film for forming a protective film are simultaneously cured, the film for forming a protective film after curing and the adhesive layer adhere to the interface to such an extent that they cannot be peeled off. In this case, it is difficult to provide a semiconductor wafer having a protective film for forming a protective film on the back surface (in this specification, a "semiconductor wafer with a protective film" in the present specification). The support sheet is peeled off, and the semiconductor wafer with the protective film cannot be picked up normally. Since the adhesive layer in the support sheet of the present invention is made non-energy line hardenability, such a problem can be surely avoided, and the semiconductor wafer with the protective film can be more easily picked up.

The effect of the case where the adhesive layer is non-energy hardening is described herein, but even if the layer in the supporting sheet which is in direct contact with the film for forming a protective film is a layer other than the adhesive layer, as long as the layer is a non-energy line The hardening property also exerts the same effect.

<<Manufacturing method of adhesive composition>>

Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4), and other adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition other than the adhesive composition can be used to constitute the aforementioned adhesive composition Each component, that is, the above-mentioned adhesive is prepared by blending a component other than the above-mentioned adhesive as needed.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

In the case of using a solvent, it may be used by mixing a solvent with any of the formulation components other than the solvent to preliminarily dilute the formulation component; or by using any of the following solvents: The formulated ingredients are pre-diluted to mix the solvent with these formulated ingredients.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by stirring a stirring blade or a stirring blade, a method of mixing using a mixer, and applying ultrasonic waves. The method of mixing, etc.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and it is preferably adjusted, and the temperature is preferably from 15 ° C to 30 ° C.

◎ Protective film forming film

In the present invention, the adhesion between the protective film obtained by curing the film for forming a protective film and the support sheet is 50 mN/25 mm to 1500 mN/25 mm, preferably 52 mN/25 mm to 1450 mN/25 mm, more preferably 53 mN/25 mm to 1430mN/25mm. When the semiconductor wafer with the protective film is picked up by the adhesive force being at least the above-described lower limit value, the semiconductor wafer with the protective film outside the target is picked up and suppressed, and the target-attached protective film can be picked up with high selectivity. Semiconductor wafer. In addition, by the aforementioned adhesive force, the foregoing Below the limit value, when the semiconductor wafer with the protective film is picked up, the crack and the defect of the semiconductor wafer are suppressed. As described above, the composite sheet for forming a protective film has a good pick-up property by the aforementioned adhesive force within a specific range.

In the present invention, even if the film for forming a protective film is cured, the laminated structure of the cured product (in other words, the support sheet and the protective film) of the support sheet and the film for forming a protective film is maintained. It is a "composite sheet for forming a protective film".

The adhesion between the protective film and the support sheet can be measured by the following method.

In other words, the composite sheet for forming a protective film having a width of 25 mm and having a predetermined length is attached to the adherend by the film for forming a protective film of the composite sheet for forming a protective film.

Then, the film for forming a protective film was cured by irradiation with an energy ray, and after forming a protective film, the support sheet was peeled off at a peeling speed of 300 mm/min from the protective film attached to the adherend. In this case, the peeling system is a so-called 180° peeling in which the surface of the protective film and the support sheet are in contact with each other at an angle of 180°, and the support sheet is along the longitudinal direction of the support sheet (the composite sheet for forming a protective film) Stripped in the length direction. Then, the load (peeling force) at the time of 180° peeling was measured, and the measured value of the load (peeling force) was defined as the above-described adhesive force (mN/25 mm).

The length of the composite sheet for forming a protective film for measurement is stable as long as it is stable The range in which the adhesion is detected is not particularly limited, and is preferably 100 mm to 300 mm. In addition, it is preferable to stabilize the attached state of the composite sheet for forming a protective film by attaching the composite sheet for forming a protective film to the adherend.

In the present invention, the adhesive force between the film for forming a protective film and the support sheet is not particularly limited, and may be, for example, 80 mN/25 mm or more, preferably 100 mN/25 mm or more, more preferably 150 mN/25 mm or more. It is 200mN/25mm or more. When the adhesive force is 100 mN/25 mm or more, the peeling of the film for forming a protective film and the support sheet at the time of dicing is suppressed, and for example, the scattering of the semiconductor wafer having the film for forming a protective film on the back surface from the support sheet is suppressed.

On the other hand, the upper limit of the adhesive force between the film for forming a protective film and the support sheet is not particularly limited, and may be, for example, any of 4000 mN/25 mm, 3500 mN/25 mm, and 3000 mN/25 mm. However, these are examples.

That is, as an aspect, the adhesion between the film for forming a protective film and the support sheet may be 80 mN/25 mm to 4000 mN/25 mm, preferably 100 mN/25 mm to 3500 mN/25 mm, and more preferably 150 mN/25 mm. Up to 3500mN/25mm, especially 200mN/25mm to 3000mN/25mm.

The adhesion between the film for forming a protective film and the support sheet can be utilized between the protective film and the support sheet described above, except that the film for forming a protective film to be measured is not cured by irradiation of the energy ray. Adhesion The same method was used for the measurement.

The adhesion between the protective film and the support sheet and the adhesive force between the film for forming a protective film and the support sheet can be adjusted, for example, by the type and amount of the component contained in the film for forming a protective film, and in the support sheet. The constituent material of the layer of the film for forming a protective film, the surface state of the layer, and the like are appropriately adjusted.

For example, the type and amount of the component contained in the film for forming a protective film can be adjusted by the type and amount of the component contained in the protective film forming composition to be described later. Further, by adjusting the content of the component of the protective film-forming composition, for example, the type and content of the polymer (b) having no energy ray-curable group, the content of the filler (d), or the crosslinking agent (f) The content of the protective film or the film for forming a protective film and the support sheet can be more easily adjusted.

In the case where the layer of the film for forming a protective film in the support sheet is an adhesive layer, the constituent material of the layer can be appropriately adjusted by adjusting the kind and amount of the component contained in the adhesive layer. Further, the type and amount of the component contained in the adhesive layer can be adjusted by the type and amount of the component contained in the above-mentioned adhesive composition.

On the other hand, when the layer of the film for forming a protective film in the support sheet is a substrate, the adhesion between the film for forming the protective film or the protective film and the support sheet is not limited to the constituent material of the substrate. The surface state of the substrate can be adjusted. And, the surface state of the substrate can be implemented, for example, by The foregoing has been adjusted as a surface treatment exemplified by the treatment for improving the adhesion between the substrate and the other layer, that is, by the embossing treatment such as blasting or solvent treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, Ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc., oxidation treatment; primer treatment or the like.

The film for forming a protective film includes a film for forming a protective film having energy ray-curable properties, for example, an energy ray-curable component (a).

The energy ray-curable component (a) is preferably uncured, preferably adhesive, more preferably uncured and adhesive.

The film for forming a protective film may be only one layer (single layer), or may be a plurality of layers of two or more layers; in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not Specially limited.

The thickness of the film for forming a protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, still more preferably from 5 μm to 50 μm. When the thickness of the film for forming a protective film is at least the above lower limit value, a protective film having a higher protective ability can be formed. In addition, when the thickness of the film for forming a protective film is equal to or less than the above upper limit value, the thickness can be suppressed from being too thick.

Here, the "thickness of the film for forming a protective film" means the thickness of the entire film for forming a protective film. For example, the thickness of the film for forming a protective film composed of a plurality of layers means the entire layer of the film for forming a protective film. Total thickness.

The curing condition when the protective film forming film is cured to form a protective film is not particularly limited as long as the protective film has a degree of hardening that sufficiently exhibits the function of the protective film, and is appropriately selected depending on the type of the protective film forming film. Just fine.

For example, when the film for forming a protective film is cured, the illuminance of the energy ray is preferably from 4 mW/cm ² to 280 mW/cm ² . Further, in the hardening, the amount of light of the energy ray is preferably from 3 mJ/cm ² to 1000 mJ/cm ² .

<<Constituent for forming a protective film>>

The film for forming a protective film can be formed using a composition for forming a protective film containing a constituent material of the film for forming a protective film. For example, a composition for forming a protective film is applied to a surface to be formed of a film for forming a protective film, and if necessary, a composition for forming a protective film is dried, whereby a film for forming a protective film can be formed at a target portion. The content ratio of the components which are not vaporized at normal temperature in the composition for forming a protective film is usually the same as the content ratio of the components in the film for forming a protective film. Here, the "normal temperature" is as described above.

The protective film-forming composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater, knife coater, bar coater, gravure coater, and roll. Coating machine, roll coater, curtain coater, die coater, knife coater, screen coater, wire bar coater, contact coater, and the like.

The drying condition of the protective film-forming composition is not particularly limited. When the protective film-forming composition contains a solvent to be described later, it is preferably heated and dried. In this case, it is preferably, for example, 70 ° C to 130 ° C. Drying is carried out for 10 seconds to 5 minutes.

<Construction film forming composition (IV-1)>

The protective film-forming composition (IV-1) or the like containing the energy ray-curable component (a) is exemplified as the protective film-forming composition.

[Energy line hardening component (a)]

The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and this component is used to impart film-forming property or flexibility to the film for forming a protective film.

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray-curable group and having a molecular weight of 100 to 80,000. (a2). At least a part of the polymer (a1) may be crosslinked by a crosslinking agent (f) to be described later, or may not be crosslinked.

In the present specification, the "weight average molecular weight" means a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

(having an energy ray-hardening group and having a weight average molecular weight of 80,000 to 2,000,000 polymer (a1))

Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1), and the acrylic resin (a1-1) is an acrylic polymer (a11). And an energy ray-curable compound (a12) having a functional group reactive with a group of another compound, wherein the energy ray-curable compound (a12) has a functional group An energy ray-curable group such as a reaction group and an energy ray-hardening double bond.

Examples of the functional group reactive with the other compound in the acrylic polymer (a11) include a hydroxyl group, a carboxyl group, an amine group, and a substituted amine group (one or two hydrogen atoms in the amine group). A group obtained by substituting a group other than a hydrogen atom, an epoxy group or the like. However, in terms of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor wafer, the functional group is preferably a group other than a carboxyl group.

Among these, the aforementioned functional group is preferably a hydroxyl group.

. Acrylic polymer having functional groups (a11)

The acrylic polymer (a11) having a functional group may, for example, be a polymer obtained by copolymerizing the acrylic monomer having a functional group and the acrylic monomer having no functional group, or may be a polymer. In addition to these monomers, a polymer obtained by copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) is further used.

In addition, the acrylic polymer (a11) may be a random copolymer, It can be a block copolymer.

Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, a substituted amine group-containing monomer, and an epoxy group-containing monomer. .

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylate; vinyl alcohol, A non-(meth)acrylic unsaturated alcohol such as allyl alcohol (that is, an unsaturated alcohol having no (meth)acryl fluorenyl skeleton).

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid such as (meth)acrylic acid or crotonic acid (that is, a monocarboxylic acid having an ethylenically unsaturated bond); fumaric acid and clothing; An ethylenically unsaturated dicarboxylic acid such as a benic acid, a maleic acid or a citraconic acid (that is, a dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the aforementioned ethylenically unsaturated dicarboxylic acid; A carboxyalkyl (meth)acrylate such as carboxyethyl ester.

The acrylic monomer having the aforementioned functional group is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, more preferably a hydroxyl group-containing monomer.

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

The acrylic monomer having no such functional group is preferably an alkyl (meth)acrylate having an alkyl group of an alkyl ester and having a chain structure of from 1 to 18, and examples thereof include, for example, Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Dibutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid 2 -ethylhexyl ester, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, Undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate), tridecyl (meth)acrylate, (meth)acrylic acid Tetradecyl ester (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as (meth)acrylic palm Ester), (meth)acrylic acid Heptadecyl ester, octadecyl (meth) acrylate (also known as stearyl (meth) acrylate), and the like.

Further, examples of the acrylic monomer having no functional group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxylated (meth)acrylate. (A) alkoxyalkyl-containing (meth) acrylate such as ester, ethoxyethyl (meth) acrylate; containing (meth) propylene (meth)acrylate having an aromatic group such as aryl (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivative; (meth)acrylic acid N, A non-crosslinkable (meth) acrylate having a tertiary amino group such as N-dimethylaminoethyl ester or N,N-dimethylaminopropyl (meth)acrylate.

The acrylic monomer having no functional group in the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

The non-acrylic monomer constituting the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the structural unit derived from the acrylic monomer having the functional group is preferably the total mass of the structural unit constituting the acrylic polymer (a11). From 0.1% by mass to 50% by mass, more preferably from 1% by mass to 40% by mass, even more preferably from 3% by mass to 30% by mass. By the above ratio being such a range, the energy ray hardening in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be achieved. The content of the base is easily adjusted to a preferred range by the degree of hardening of the first protective film.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

. Energy line hardening compound (a12)

The energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group, and is compatible with the acrylic polymer (a11). The group of the functional group reaction is more preferably an isocyanate group as the above group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the above-mentioned group, the isocyanate group is easily reacted with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.

The energy ray-curable compound (a12) preferably has one to five of the energy ray-curable groups in one molecule, and more preferably has one to three energy ray-curable groups.

Examples of the energy ray-curable compound (a12) include 2-methylpropenyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and methacryl Isocyanate, allyl isocyanate, 1,1-(bispropenyloxymethyl)ethyl isocyanate; by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate Acrylate-based monoisocyanate compound obtained; by diisocyanate An acrylonitrile monoisocyanate compound obtained by a reaction of a compound or a polyisocyanate compound, a polyol compound, and a hydroxyethyl (meth)acrylate.

Among these, the energy ray-curable compound (a12) is preferably 2-methylpropenyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

The content of the acrylic resin (a1-1) is preferably from 1% by mass to 40% by mass, and more preferably from 2% by mass to 30%, based on the total mass of the solvent in the protective film-forming composition (IV-1). The mass% is particularly preferably from 3% by mass to 20% by mass.

In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the aforementioned functional group derived from the acrylic polymer (a11) It is preferably from 20 mol% to 120 mol%, more preferably from 35 mol% to 100 mol%, still more preferably from 50 mol% to 100 mol%. By the above content ratio being such a range, the adhesion force of the protective film formed by hardening becomes larger. In the case where the energy ray-curable compound (a12) is a monofunctional compound (having one of the above-mentioned groups in one molecule), the upper limit of the ratio of the content is 100 mol%, but the energy is The linear curable compound (a12) is polyfunctional (in 1 minute) In the case where the compound has two or more of the above-mentioned groups, the upper limit of the ratio of the above content may exceed 100 mol%.

The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1,500,000.

When at least a part of the polymer (a1) is crosslinked by a crosslinking agent (f), the polymer (a1) may be any one of the acrylic polymers (a11) which does not conform to the above description. The monomer having a monomer reactive with the crosslinking agent (f) is polymerized, crosslinked in a group reactive with the above crosslinking agent (f), or may be derived from the aforementioned energy ray-curable compound (a12) Crosslinking is carried out in the group reactive with the aforementioned functional groups.

The polymer (a1) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these combinations may be used. And the ratio can be arbitrarily chosen.

(Compound (a2) having an energy ray-hardening group and having a molecular weight of 100 to 80,000)

Examples of the energy ray-curable group of the compound (a2) having an energy ray-curable group and having a molecular weight of from 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred examples of the group include (A) Base) acrylonitrile, vinyl, and the like.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, and an energy ray-curable group. Phenolic resin, etc.

In the compound (a2), the low molecular weight compound having an energy ray-curable group may, for example, be a polyfunctional monomer or oligomer, and is preferably an acrylate-based compound having a (meth) acrylonitrile group.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylate. Bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)propenyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) Acrylate, 2,2-bis[4-((meth)propenyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(methyl)propenyloxy) Ethoxy)phenyl]anthracene, 2,2-bis[4-((meth)propenyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (also It is called tricyclodecane dimethylol di(meth) acrylate), 1,10-nonanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1 , 9-decanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di( Methyl) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, 2,2-bis [4-( (Meth) propylene methoxy ethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1, 3 -two Bifunctional (meth) acrylate such as (meth) propylene decyloxypropane; tris(2-(methyl) propylene oxyethyl) isocyanurate, ε-caprolactone modified isocyanurate Tris-(2-(methyl)propenyloxyethyl) acid, ethoxylated glycerol tri(meth) acrylate, pentaerythritol tri(meth) acrylate, trimethylolpropane tris(methyl) Acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate A polyfunctional (meth) acrylate oligomer such as dipentaerythritol hexa(meth) acrylate or a polyfunctional (meth) acrylate oligomer such as a (meth) acrylate urethane oligomer.

In the above-mentioned compound (a2), as the epoxy resin having an energy ray-curable group or a phenol resin having an energy ray-curable group, for example, paragraph 0043 in "Japanese Patent Laid-Open Publication No. 2013-194102" can be used. Resin. Such a resin also conforms to the resin constituting the thermosetting component (h) to be described later, but in the present invention, the compound (a2) is regarded.

The aforementioned compound (a2) preferably has a weight average molecular weight of from 100 to 30,000, more preferably from 300 to 10,000.

The compound (a2) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. In the case of two or more types, these combinations and The ratio can be arbitrarily chosen.

[Polymer without energy line hardening group (b)]

When the protective film-forming composition (IV-1) and the film for forming a protective film contain the compound (a2) as the energy ray-curable component (a), it is preferable to further contain no energy ray curability. Base polymer (b).

The polymer (b) may be crosslinked at least in part by the crosslinking agent (f) or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, and an urethane urethane resin. , polyvinyl alcohol (PVA), butyral resin, polyester urethane resin, and the like.

Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, simply referred to as "acrylic polymer (b-1)").

The acrylic polymer (b-1) may be a known polymer, and may be, for example, a homopolymer of one type of acrylic monomer, or a copolymer of two or more types of acrylic monomers, or one type or A copolymer of two or more kinds of acrylic monomers and one or more monomers (non-acrylic monomers) other than the acrylic monomers.

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include an alkyl (meth)acrylate, a (meth)acrylate having a cyclic skeleton, and a glycidyl group (A). Acrylate, hydroxyl group-containing (meth) acrylate, substituted amino group-containing (meth) acrylate, and the like. this The term "substituted amino group" means a group in which one or two hydrogen atoms in the amine group are substituted by a group other than a hydrogen atom.

The alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having an alkyl group of an alkyl ester and having a chain structure of from 1 to 18, and examples thereof include (meth) ) methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ( Dibutyl methacrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl ester, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, ( Undecyl (meth) acrylate, lauryl (meth) acrylate (also known as lauryl (meth) acrylate), tridecyl (meth) acrylate, (meth) acrylate Tetraalkyl ester (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as palmityl (meth)acrylate ), heptadecyl (meth) acrylate , (Meth) acrylate, stearyl acrylate (also known as (meth) acrylate, stearyl acrylate) and the like.

Examples of the (meth) acrylate having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; Arylalkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth) acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate (meth)acrylic acid cycloolefin Oxyalkyl esters and the like.

Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth)acrylate and the like.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (methyl). 3 - hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

Examples of the (meth) acrylate containing a substituted amino group include N-methylaminoethyl (meth) acrylate and the like.

The non-acrylic monomer constituting the acrylic polymer (b-1) may, for example, be an olefin such as ethylene or norbornene; vinyl acetate; styrene or the like.

As the polymer (b) which is crosslinked by at least a part of the crosslinking agent (f) and does not have the aforementioned energy ray-curable group, for example, a reactive functional group and a crosslinking agent in the above polymer (b) (f) a polymer of the reaction.

The reactive functional group is appropriately selected depending on the type of the crosslinking agent (f), and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, the reactive functional group may, for example, be a hydroxyl group, a carboxyl group or an amine group; and among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. Further, when the crosslinking agent (f) is an epoxy compound, Examples of the reactive functional group include a carboxyl group, an amine group, and a guanamine group. Among them, a carboxyl group having high reactivity with an epoxy group is preferred. However, in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.

The polymer (b) having the reactive functional group and having no energy ray-curable group may, for example, be a polymer obtained by polymerizing at least a monomer having the reactive functional group. In the case of the acrylic polymer (b-1), either or both of the acrylic monomer and the non-acrylic monomer exemplified as the monomer constituting the acrylic polymer (b-1) A monomer having the aforementioned reactive functional group may be used. For example, as the polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate may be mentioned, and other examples thereof may be mentioned. A polymer obtained by polymerizing a monomer in which one or two or more hydrogen atoms of the acrylic monomer or non-acrylic monomer are substituted with the reactive functional group.

In the above polymer (b) having a reactive functional group, the ratio (content) of the structural unit derived from the monomer having a reactive functional group is preferably relative to the total mass of the structural unit constituting the polymer (b). It is 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass. By the above ratio being such a range, in the polymer (b), the degree of crosslinking is in a more preferable range.

The film forming property of the protective film forming composition (IV-1) is more excellent. The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000.

The polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more kinds; In the above cases, these combinations and ratios can be arbitrarily selected.

The composition (IV-1) for forming a protective film includes a composition containing either or both of the polymer (a1) and the compound (a2). Further, when the protective film-forming composition (IV-1) contains the compound (a2), it is preferred to further contain the polymer (b) having no energy ray-curable group; in this case, Jia further contains the aforementioned (a1). In addition, the protective film-forming composition (IV-1) may not contain the compound (a2), and may contain the polymer (a1) and the polymer (b) having no energy ray-curable group.

When the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the protective film-forming composition ( The content of the compound (a2) in the above IV-1) is preferably from 10 parts by mass to 100 parts by mass based on 100 parts by mass of the total of the polymer (a1) and the polymer (b) having no energy ray-curable group. The parts by mass are more preferably from 30 parts by mass to 350 parts by mass.

In the protective film-forming composition (IV-1), the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in terms of the total content of components other than the solvent ( In other words, the total content (mass) of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group with respect to the total mass of the film for forming a protective film is preferably 5% by mass. It is 90% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 15% by mass to 70% by mass. When the ratio of the total content is in such a range, the energy ray hardenability of the film for forming a protective film becomes better.

When the protective film-forming composition (IV-1) contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) In the film for forming a protective film, the content of the polymer (b) is preferably from 3 parts by mass to 160 parts by mass, more preferably 6 parts by mass, per 100 parts by mass of the content of the energy ray-curable component (a). Up to 130 parts by mass. When the content of the polymer (b) is in such a range, the energy ray hardenability of the film for forming a protective film becomes better.

In the protective film-forming composition (IV-1), in addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, it may be selected from a photopolymerization initiator according to the purpose. (c), a filler (d), a coupling agent (e), a crosslinking agent (f), a coloring agent (g), a thermosetting component (h), and a general additive (z) One or two or more. For example, by using the protection containing the aforementioned energy ray hardening component (a) and thermosetting component (h) In the film-forming composition (IV-1), the film for forming a protective film to be formed is improved in adhesion to the adherend by heating, and the strength of the protective film formed of the film for forming a protective film is also improved.

[Photopolymerization initiator (c)]

Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetophenone compound; fluorenylphosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide a sulfonate compound such as benzyl phenyl sulfide or tetramethyl thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; Isoferrocene compound; thioxanthone compound such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholineylphenyl)-2-benzyl- 1-butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) Equivalent benzophenone compound; peroxide compound; diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; 2,4-diethyl Thioxanthone: 1,2-diphenyl methane; hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloro-anthraquinone.

Further, as the photopolymerization initiator (c), for example, a ruthenium compound such as 1-chloroindole or a photosensitizer such as an amine can be used.

The photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be one type or two or more types. When two or more types are used, these combinations and ratios may be arbitrary. select.

In the case of using the photopolymerization initiator (c), the content of the photopolymerization initiator (c) in the composition for forming a protective film (IV-1) relative to the content of the energy ray-curable compound (a) is 100. The parts by mass are preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass to 10 parts by mass, still more preferably from 0.05 part by mass to 5 parts by mass.

[filler (d)]

When the film for forming a protective film contains the filler (d), the protective film obtained by curing the film for forming a protective film is easily adjusted in thermal expansion coefficient, and the coefficient of thermal expansion is optimized for the object to be formed of the protective film. The reliability of the package obtained by the composite sheet for forming a protective film is further improved. Further, when the film for forming a protective film contains the filler (d), the moisture absorption rate of the protective film can be lowered or the heat dissipation property can be improved.

As the filler (d), for example, a material composed of a thermally conductive material can be cited.

The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

Examples of preferred inorganic fillers include cerium oxide, aluminum oxide, talc, calcium carbonate, titanium white, iron oxide, tantalum carbide, boron nitride, and the like. Powder; beads obtained by spheroidizing these inorganic filler materials; surface modification products of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers and the like.

Among these, the inorganic filler is preferably cerium oxide or aluminum oxide.

The average particle diameter of the filler (d) is not particularly limited, but is preferably from 0.01 μm to 20 μm, more preferably from 0.1 μm to 15 μm, still more preferably from 0.3 μm to 10 μm. When the average particle diameter of the filler (d) is in such a range, the adhesion to the object to be formed of the protective film can be maintained, and the decrease in the transmittance of light of the protective film can be suppressed.

In the present specification, the "average particle diameter" means the value of the particle diameter (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method unless otherwise specified. .

The filler (d) which is contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more kinds; in the case of two or more types, these combinations and The ratio can be arbitrarily chosen.

In the case of using the filler (d), the content of the filler (d) in the total amount (total mass) of all the components other than the solvent in the protective film-forming composition (IV-1) (that is, The content of the filler (d) relative to the total mass of the film for forming a protective film is preferably from 5% by mass to 83% by mass, more preferably from 7% by mass to 78% by mass. By the content of the filler (d) being such a range, it is easier to adjust the above thermal expansion coefficient.

[coupler (e)]

By using a coupling agent having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (e), the adhesion of the film for forming a protective film to the adherend and the adhesion can be improved. In addition, by using the coupling agent (e), the protective film obtained by curing the film for protective film formation is not resistant to heat resistance and water resistance is improved.

The coupling agent (e) is preferably a compound having a functional group reactive with a functional group having an energy ray-curable component (a) and a polymer (b) having no energy ray-curable group, and more preferably a decane. Coupling agent.

Preferred examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl group. Triethoxy decane, 3-glycidoxymethyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino)propyltrimethoxydecane, 3-(2-aminoethylamino)propylmethyl Diethoxydecane, 3-(phenylamino)propyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyltrimethyl Oxydecane, 3-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide, methyltrimethoxydecane, methyltriethoxydecane, ethylene Trimethoxy decane, vinyl triethoxy decane, imidazolium, and the like.

The coupling agent (IV) and the protective film forming film may be used alone or in combination of two or more kinds. The ratio can be arbitrarily chosen.

In the case of using the coupling agent (e), the protective film-forming composition (IV-1) and the film for forming a protective film have a content of the coupling agent (e) with respect to the energy ray-curable component (a) and The total content of the energy ray-curable group-containing polymer (b) is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, still more preferably 0.1 part by mass to 5 parts by mass. . When the content of the coupling agent (e) is at least the above lower limit value, it is possible to obtain a more remarkable effect by using the coupling agent (e): the dispersibility of the filler (d) in the resin is improved, and the like. Or the adhesion between the film for forming a protective film and the adherend is improved. Further, when the content of the coupling agent (e) is at most the above upper limit value, generation of outgas can be further suppressed.

[crosslinking agent (f)]

By using the crosslinking agent (f), the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group is crosslinked, whereby the initial adhesion of the film for forming a protective film can be adjusted. And cohesion.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine crosslinking. A reagent (a cross-linking agent having an aziridine group) or the like.

Examples of the organic polyvalent isocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds"); a trimer such as an aromatic polyisocyanate compound, an isocyanurate body or an adduct, a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound or the like with a polyol compound, and the like . The term "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and is contained in ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. The reactant of the compound of the low molecular weight active hydrogen, as an example of the above-mentioned adduct, may be a benzodimethyl diisocyanate adduct of trimethylolpropane mentioned later. Further, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a terminal portion of the molecule.

As the above-mentioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-benzenedimethyl diisocyanate; 1,4-dimethylbenzene Isocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; polyhydric alcohol such as trimethylolpropane A compound obtained by adding one or two or more kinds of toluene diisocyanate, hexamethylene diisocyanate, and benzene dimethyl diisocyanate; or a dibasic acid diisocyanate.

The organic polyimine compound may, for example, be N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide) or trimethylolpropane-tri-beta-nitrogen. Propidyl propionate, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarbamamine) Based on melamine and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferred to use a hydroxyl group-containing polymer as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group. . When the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray are used. The reaction of the curable component (a) or the polymer (b) having no energy ray-curable group can easily introduce the crosslinked structure into the film for forming a protective film.

The crosslinking agent (f) contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these combinations may be used. And the ratio can be arbitrarily chosen.

When the crosslinking agent (f) is used, the protective film forming composition In (IV-1), the content of the crosslinking agent (f) is preferably 0.01 by mass based on 100 parts by mass of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group. The parts by mass are 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, still more preferably 0.5 parts by mass to 5 parts by mass. When the content of the crosslinking agent (f) is at least the above lower limit value, a more remarkable effect by the use of the crosslinking agent (f) can be obtained. Further, when the content of the crosslinking agent (f) is at most the above upper limit value, excessive use of the crosslinking agent (f) can be suppressed.

[coloring agent (g)]

Examples of the colorant (g) include known coloring agents such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigment and the organic dye include an ammonium dye, a cyanine dye, a merocyanine dye, a croconium dye, a squalilium dye, and an anthraquinone. Pigment, polymethine dye, naphthoquinone dye, pyryl quinone dye, phthalocyanine dye, naphthalocyanine dye, naphthalene amide dye, azo dye, condensed azo dye, indigo a pigment, a perinone dye, a merging dye, a dioxane dye, a quinacridone dye, an isoindolinone dye, a quinophthalone pigment, a pyrrole dye, A thioindigo dye, a metal complex dye (metal stear salt dye), a dithiol metal complex dye, a nonylphenol dye, a triallylmethane dye, an anthraquinone dye, a naphthol A coloring matter, a methine azo dye, a benzimidazolone dye, a swainone pigment, and a threne pigment.

Examples of the inorganic pigment include carbon black, a cobalt dye, an iron dye, a chromium dye, a titanium dye, a vanadium dye, a zirconium dye, a molybdenum dye, an anthraquinone dye, a platinum dye, and ITO. (Indium Tin Oxide; indium tin oxide) dye, ATO (Antimony Tin Oxide) pigment, and the like.

The coloring agent (g) contained in the film for forming a protective film (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these combinations and The ratio can be arbitrarily chosen.

In the case of using the coloring agent (g), the content of the coloring agent (g) in the film for forming a protective film may be appropriately adjusted depending on the purpose. For example, in the case where printing is applied to the protective film by laser irradiation, the print visibility can be adjusted by adjusting the content of the coloring agent (g) in the film for forming a protective film and adjusting the light transmittance of the protective film. In this case, the content of the coloring agent (g) in the total content of all the components other than the solvent in the protective film-forming composition (IV-1) (that is, the total mass of the film for forming a protective film) The content of the colorant (g) is preferably from 0.1% by mass to 10% by mass, more preferably from 0.4% by mass to 7.5% by mass, even more preferably from 0.8% by mass to 5% by mass. When the content of the coloring agent (g) is at least the above lower limit value, a more remarkable effect by the use of the coloring agent (g) can be obtained. In addition, when the content of the coloring agent (g) is at most the above upper limit value, excessive use of the coloring agent (g) can be suppressed.

[thermosetting component (h)]

The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these are Combinations and ratios can be arbitrarily chosen.

Examples of the thermosetting component (h) include an epoxy thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, a polyoxyl resin, and the like. Epoxy thermosetting resin.

(epoxy thermosetting resin)

The epoxy thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).

The epoxy-based thermosetting resin contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these are Combinations and ratios can be arbitrarily chosen.

. Epoxy resin (h1)

Examples of the epoxy resin (h1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolac epoxy. Two or more epoxy resins such as resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenyl skeleton type epoxy resin Compound.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained by using the composite sheet for forming a protective film is improved by using an epoxy resin having an unsaturated hydrocarbon group.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy group of the polyfunctional epoxy resin is replaced with a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group.

In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include a secondary ethyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and (a). The acrylonitrile group, the (meth) acrylamide group, and the like are preferably an acrylonitrile group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, and is preferably from 300 to 30,000, more preferably from 400 to 3, in terms of the curability of the film for forming a protective film and the strength and heat resistance of the protective film. 10,000, especially 500 to 3000.

In the present specification, the term "number average molecular weight" means, unless otherwise specified, a gel permeation chromatography (GPC) method and standard polyphenylene. The value in terms of ethylene indicates the number average molecular weight.

The epoxy equivalent of the epoxy resin (h1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 150 g/eq to 800 g/eq.

In the present specification, the term "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, which can be measured in accordance with the method of JIS K 7236:2001.

The epoxy resin (h1) may be used singly or in combination of two or more. When two or more kinds are used in combination, these combinations and ratios may be arbitrarily selected.

. Thermal hardener (h2)

The heat hardener (h2) functions as a hardener for the epoxy resin (h1).

The thermosetting agent (h2) is, for example, a compound having two or more functional groups reactive with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and a group in which an acid group is anhydride-formed. Preferably, the phenolic hydroxyl group, the amine group, or the acid group is anhydride-treated. More preferably, it is a phenolic hydroxyl group or an amine group.

In the thermosetting agent (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, a biphenol, a novolak type phenol resin, a dicyclopentadiene type phenol resin, and an aralkylphenol. Resin, etc.

In the thermosetting agent (h2), examples of the amine-based curing agent having an amine group include dicyandiamide (hereinafter sometimes abbreviated as "DICY").

The heat hardener (h2) may also have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group in which an aromatic ring of the phenol resin is directly bonded to have an unsaturated hydrocarbon group. Compounds and the like.

The aforementioned unsaturated hydrocarbon group in the heat hardener (h2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermosetting agent (h2), the thermosetting agent (h2) is preferably a phenol having a softening point or a high glass transition temperature in terms of improving the peeling property of the protective film from the support sheet. A hardener.

In the thermal curing agent (h2), the resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin preferably has a number average molecular weight of 300 to 30,000, more preferably It is 400 to 10,000, and particularly preferably 500 to 3,000.

In the thermal curing agent (h2), the molecular weight of the non-resin component such as biphenol or dicyandiamide is not particularly limited, and is, for example, preferably 60 to 500.

The heat-hardening agent (h2) can be used singly or in combination of two or more kinds. When two or more types are used in combination, these combinations and ratios can be arbitrarily selected.

When the thermosetting component (h) is used, the protective film forming group In the film (IV-1) and the film for forming a protective film, the content of the thermosetting agent (h2) is preferably 0.01 parts by mass to 20 parts by mass based on 100 parts by mass of the epoxy resin (h1).

When the thermosetting component (h) is used, the content of the thermosetting component (h) in the protective film-forming composition (IV-1) and the film for forming a protective film (for example, epoxy resin (h1)) The content of the total amount of the thermosetting agent (h2) is preferably from 1 part by mass to 500 parts by mass based on 100 parts by mass of the polymer (b) having no energy ray-curable group.

[General Additives (z)]

The general-purpose additive (z) can be a known general-purpose additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives include plasticizers, antistatic agents, antioxidants, getters, and the like. .

The general additive (z) contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these combinations and The ratio can be arbitrarily chosen.

In the case of using the general-purpose additive (z), the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the film for forming a protective film is not particularly limited, and may be appropriately selected according to the purpose.

[solvent]

The protective film-forming composition (IV-1) preferably further contains a solvent. The handling property (IV-1) for forming a protective film containing a solvent is excellent in handleability.

The solvent is not particularly limited, and examples of preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1 - an alcohol such as butanol; an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; a decylamine such as dimethylformamide or N-methylpyrrolidone (a compound having a guanamine bond) )Wait.

The solvent contained in the protective film-forming composition (IV-1) may be one type or two or more types. When two or more types are used, these combinations and ratios can be arbitrarily selected.

The solvent contained in the protective film-forming composition (IV-1) is preferably methyl ethyl ketone, in that the component contained in the protective film-forming composition (IV-1) is more uniformly mixed. , toluene or ethyl acetate.

<<Method for Producing Composition for Protective Film Formation>>

The protective film forming composition such as the protective film-forming composition (IV-1) is obtained by blending the components constituting the protective film-forming composition.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

In the case of using a solvent, it may be used by mixing a solvent with any of the formulation components other than the solvent to preliminarily dilute the formulation component; or by using any of the following solvents: The formulated ingredients are pre-diluted to mix the solvent with these formulated ingredients.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by stirring a stirring blade or a stirring blade, a method of mixing using a mixer, and applying ultrasonic waves for mixing. Method and so on.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and it is preferably adjusted, and the temperature is preferably from 15 ° C to 30 ° C.

In the same manner as the composite sheet for forming a protective film of the present invention, it is a composite sheet which is attached to a back surface of a semiconductor wafer or a semiconductor wafer which is opposite to the circuit surface and which has a layer which exhibits adhesion on the support sheet. Sticky wafer.

However, the adhesive layer provided in the diced wafer has a function of being used as an adhesive when the semiconductor wafer is mounted on a substrate, a lead frame, or another semiconductor wafer, together with the semiconductor wafer. On the other hand, the film for forming a protective film in the composite sheet for forming a protective film of the present invention is the same as the above-mentioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but is finally cured by curing. The protective film has the function of protecting the back side of the attached semiconductor wafer. As described above, the use of the film for forming a protective film in the present invention is different from that of the adhesive layer in the diced bonded wafer, and of course the required performance is also different. Further, in general, when the difference in the application is compared with the adhesive layer in the crystal-cut wafer, the film for forming a protective film tends to be hard and difficult to pick up. Therefore, it is often difficult to directly transfer the adhesive layer in the crystal-cut wafer to the protective film. A film for forming a protective film in the composite sheet for forming. The composite sheet for forming a protective film of the present invention is provided with an energy ray-curable film for forming a protective film, and the pick-up property of the semiconductor wafer with the protective film is extremely excellent.

Method for producing ruthenium film for forming protective film

The composite sheet for forming a protective film of the present invention can be produced by sequentially laminating the above layers in a corresponding positional relationship. The formation method of each layer is as described above.

For example, when the support sheet is produced, when the adhesive layer is laminated on the substrate, the adhesive composition is applied onto the substrate, and the adhesive composition may be dried as needed. Further, a light shielding layer may be provided on the substrate in advance by a printing method or the like.

On the other hand, for example, when a film for forming a protective film is laminated on an adhesive layer which is laminated on a substrate, a film for forming a protective film can be applied onto the adhesive layer to directly form a film for forming a protective film. A layer other than the film for forming a protective film may be used to form a composition of the layer, and the layer may be laminated on the adhesive layer by the same method. Thus, in the case where a laminated structure of two consecutive layers is formed using any of the compositions, the composition can be further coated on the layer formed of the above composition to newly form a layer.

However, it is preferable to form a continuous two-layer laminated structure by previously forming a layer of the two-layer back-layered layer on the other release film using the above-mentioned composition, and to form the layer in the formed layer. The exposed side opposite to the side on which the peeling film is in contact with the exposed side of the remaining layer formed Hehe. In this case, the composition is preferably applied to the release-treated surface of the release film. After forming the laminate structure, the release film may be removed as needed.

For example, a composite sheet for forming a protective film formed by laminating an adhesive layer on a substrate and a film for forming a protective film on the adhesive layer (the support sheet is formed of a protective film of a laminate of a substrate and an adhesive layer). In the case of a composite sheet), an adhesive composition is applied to a substrate, and the adhesive composition is dried as needed to preliminarily deposit an adhesive layer on the substrate; and a protective film is formed on the release film to form a composition. The film for the protective film formation is dried as needed, and a film for forming a protective film is formed in advance on the release film. Then, the exposed surface of the film for forming a protective film is bonded to the exposed surface of the adhesive layer deposited on the substrate, and a film for forming a protective film is laminated on the adhesive layer to obtain a composite sheet for forming a protective film. .

Further, when the adhesive layer is laminated on the substrate, as described above, the adhesive composition may be applied to the release film instead of applying the adhesive composition on the substrate, and the adhesive may be composed as needed. The material is dried, whereby an adhesive layer is formed in advance on the release film, and the exposed surface of the layer is bonded to one surface of the substrate, whereby an adhesive layer is laminated on the substrate.

In either method, the release film may be removed at any point after the formation of the target laminate structure.

In this way, the layer other than the base material constituting the composite sheet for forming a protective film can be laminated by the following method: it is formed on the release film in advance, and is then bonded to the target. Since the surface of the layer is appropriately selected as needed, a composite sheet for forming a protective film can be produced.

In addition, the composite sheet for forming a protective film is usually stored in a state in which a peeling film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) on the opposite side of the support sheet in the composite sheet for forming a protective film. status. Therefore, a composite sheet for forming a protective film can be obtained by coating a protective film forming composition or the like on the release film (preferably, a release-treated surface of the release film) to form a composition. The composition of the layer of the surface layer is dried, and the layer constituting the outermost layer is formed in advance on the release film, and the exposed surface on the opposite side to the side in contact with the release film in the layer is used. Either way, the remaining layers are laminated, and the peeling film is not removed to maintain the bonding state.

In the present invention, even if the film for forming a protective film is cured, the laminated structure of the cured product (in other words, the support sheet and the protective film) of the support sheet and the film for forming a protective film is maintained. It is called "composite sheet for forming a protective film".

In the same manner as the composite sheet for forming a protective film of the present invention, a composite sheet which is attached to a back surface of a semiconductor wafer or a semiconductor wafer opposite to the circuit surface and has a layer on the support sheet which exhibits adhesion is provided. Cut crystal bonded wafers.

However, regarding the adhesive layer and semiconductor of the die-cut adhesive wafer After the wafer is picked up from the support sheet, the semiconductor wafer is mounted on a substrate, a lead frame, or another semiconductor wafer, and the like functions as an adhesive. On the other hand, the film for forming a protective film which can be used in the composite sheet for forming a protective film of the present invention is the same as the above-mentioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but is finally hardened. The protective film has a function of protecting the back surface of the attached semiconductor wafer. As described above, the use of the film for forming a protective film in the present invention is different from that of the adhesive layer in the diced bonded wafer, and the required performance is of course different. Further, in general, when the film for forming a protective film is compared with the adhesive layer in the crystal-cut bonded wafer, it is difficult to pick up the difference in the use. Therefore, it is generally difficult to directly convert the adhesive layer in the crystal-cut wafer to the film for forming a protective film in the composite sheet for forming a protective film. The composite sheet for forming a protective film which can be used in the film for forming an energy ray-curable protective film of the present invention is required to have a composite sheet for forming a protective film which is excellent in pick-up property of a semiconductor wafer to which a protective film is attached.

◎ Protective film forming sheet

In the present invention, the film for forming a protective film may be used in the form of the above-mentioned composite sheet for forming a protective film, or may be provided with a protective film on the release film in the method for producing a semiconductor wafer with a protective film to be described later. After the film for forming a protective film for forming a film is attached to the back surface of the semiconductor wafer, a support sheet is attached and used.

The film for forming a protective film which can be used herein is as described in the item of the above-mentioned composite sheet for forming a protective film.

FIG. 7 is a cross-sectional view showing an embodiment of the protective film forming sheet 2F which can be used in the method for producing a semiconductor wafer with a protective film to be described later.

The protective film forming sheet 2F is provided with a protective film forming film 13 on the first release film 15' and a second release film 15" on the protective film forming film 13.

The protective film forming sheet 2F shown in Fig. 7 is used in the surface 13a of the protective film forming film 13 in a state where the second peeling film 15" is removed (that is, the protective film forming film 13). A part of the center side of the surface on the side of the second peeling film 15" is attached to the back surface of the semiconductor wafer (not shown), and the protective film is further removed in a state where the first peeling film 15' is removed. The surface 13b opposite to the surface 13a of the formation film 13 (that is, the surface on the side of the protective film formation film 13 on the side including the first release film 15') is attached to the substrate sheet, and the film for forming a protective film is formed. A region near the peripheral portion of the 13 is attached to a jig such as a ring frame.

Method for manufacturing semiconductor wafer with protective film

A method of manufacturing a semiconductor wafer with a protective film according to an aspect of the present invention will be described with reference to FIG.

A method of manufacturing a semiconductor wafer with a protective film according to an aspect of the present invention is as follows: a semiconductor in a laminated body including a support sheet 10, an energy ray-curable protective film forming film 13 and a semiconductor wafer 18; The wafer 18 is diced, and then the portion of the adhesion film of the semiconductor wafer 18 other than the region near the peripheral portion of the film 13 for forming a protective film is irradiated with energy. On the support sheet 10, a semiconductor wafer 19 with a protective film is formed on the support sheet 10, and the semiconductor wafer 19 with the protective film is picked up.

The support sheet 10 is composed of a substrate 11, an adhesive layer 12, and a light shielding layer 24, and is formed on the lower portion of the substrate 11 (that is, on the side opposite to the side of the substrate 11 on which the adhesive layer is provided) and the periphery of the support sheet 10. A region near the portion is provided with a light shielding layer 24 composed of a circular printed layer.

In other words, after the composite sheet for forming a protective film is attached to the back surface of the semiconductor wafer (the surface opposite to the surface on which the electrode is formed), the semiconductor wafer is separated from the film for forming a protective film by dicing to form a semiconductor wafer. . Then, in the film for forming a protective film to be divided, the portion of the semiconductor wafer to be adhered to the region other than the region in the vicinity of the peripheral portion is irradiated with an energy ray, and the film for forming a protective film is cured to form a protective film. Further, the laminate formed of the support sheet and the protective film is expanded in the surface direction (in the direction of the surface) of the laminate, that is, so-called expansion, and the semiconductor wafer with the protective film attached thereon is kept attached. In the state of the protective film, it is directly (that is, in the form of a semiconductor wafer with a protective film) pulled away from the support sheet and picked up.

Alternatively, the protective film forming film and the base material sheet may be attached to the semiconductor wafer without using the composite sheet for forming a protective film. In this case, the protective film forming film and the base material sheet may be formed by using the protective film described above. The film for forming a protective film and the substrate sheet described in the description of the composite sheet.

In addition, a semiconductor wafer with a protective film according to an embodiment of FIG. In the manufacturing method, the support sheet 10 includes the light-shielding layer 24 which is formed of a ring-shaped printing layer. However, the present invention is not limited thereto, and a semiconductor wafer other than the region near the peripheral portion of the protective film forming film 13 may be used. The attachment area of the 18 is irradiated with energy rays through the shielding plate.

As the shielding plate, it is preferable that the inner side is hollowed out to have a circular shape. The diameter of the hollowed out circle is preferably from 95% to 140%, more preferably from 98% to 135%, and even more preferably from 100% to 130% of the outer diameter of the semiconductor wafer. As the shielding plate, for example, an annular shielding plate made of SUS (stainless steel) can be used.

The shielding plate is used to shield a region in the vicinity of a peripheral portion of the film for forming a protective film when the energy-sensitive film is applied to the film for forming a protective film, and to attach a portion of the semiconductor wafer to the film for forming a protective film. Irradiate the energy line. When the inner side of the shielding plate has a circular shape, the diameter of the hollowed out circular is set to be 95% or more of the outer diameter of the semiconductor wafer because there is a possibility that even if the outer periphery of the semiconductor wafer is present It is slightly blocked by the shielding plate, and it is only impossible to pick up an unnecessary wafer (ie, a triangular wafer) at the end of the semiconductor wafer without causing a problem.

A method of manufacturing a semiconductor wafer with a protective film according to another aspect of the present invention will be described with reference to FIG.

A method for producing a semiconductor wafer with a protective film according to another aspect of the present invention is as follows: a protective film for forming a protective film for forming a support sheet or an energy ray-curable layer, and a laminate of a semiconductor wafer, and the protective film are provided. The semiconductor wafer is cut after irradiating the energy line with the portion of the adhesion region of the semiconductor wafer other than the region near the peripheral portion in the film for formation On the support sheet, a semiconductor wafer with a protective film is formed thereon, and the semiconductor wafer with the protective film is picked up.

In other words, the protective film forming composite sheet comprising the protective film forming film 13 and the protective film forming film 13 is attached to the semiconductor wafer by the protective film forming film 13 of the protective film forming composite sheet. The back surface of 18 (the surface opposite to the electrode forming surface). Then, the film 13 for forming a protective film is irradiated with an energy ray, and the film 13 for forming a protective film is cured to form a protective film 13'.

Next, by cutting, the semiconductor wafer 18 is divided together with the protective film 13' to form a semiconductor wafer 19 with a protective film. Then, the so-called stretching is performed, and even the laminated body composed of the supporting sheet and the protective film is spread in the surface direction (in the direction of the surface) of the laminated body, and the protective film-attached semiconductor wafer is attached and protected. In the state of the film, it is directly (that is, in the form of a semiconductor wafer 19 with a protective film) pulled away from the support sheet 10 to be picked up.

Alternatively, the protective film forming film and the base material sheet may be attached to the semiconductor wafer without using the composite sheet for forming a protective film. In this case, the protective film forming film and the base material sheet may be formed by using the protective film described above. The film for forming a protective film and the substrate sheet described in the description of the composite sheet.

Further, in the method of manufacturing a semiconductor wafer with a protective film according to the embodiment of FIG. 9, the support sheet 10 includes the light shielding layer 24 composed of a ring-shaped printing layer, but the invention is not limited thereto, and the protective film may be formed. The portion of the attachment region of the semiconductor wafer 18 other than the region near the peripheral portion of the film 13 The energy lines are illuminated via a shield.

As the shielding plate, it is preferable that the inner side is hollowed out to have a circular shape. The preferred size of the diameter of the hollowed out circle is the same as described above. As the shielding plate, for example, an annular shielding plate made of SUS can be used.

◇Semiconductor device manufacturing method

In the following, the obtained semiconductor wafer with the protective film is directly pulled out from the support sheet while being attached to the protective film by the same method as in the prior art, and the obtained protective film is attached. The semiconductor wafer of the semiconductor wafer is flip-chip bonded to the circuit surface of the substrate to form a semiconductor package. Then, the target semiconductor device can be fabricated using the semiconductor package.

In one aspect of the composite sheet for forming a protective film according to the embodiment of the present invention, the composite sheet for forming a protective film is provided, and the film for protective film formation having an energy ray-curable property is provided on the support sheet; and the support sheet is a substrate. a layered body of the pressure-sensitive adhesive layer and the light-shielding layer; wherein the light-shielding layer is an annular printed layer and is provided in a region in the vicinity of the peripheral portion of the support sheet.

Further, in the composite sheet for forming a protective film, the substrate may be a polypropylene film or a polyvinyl chloride film; and the light transmittance of the light shielding layer may be 50% or less, preferably 10%. In the following, the film for forming a protective film is a film for forming a protective film comprising an energy ray-curable component (a), a polymer having no energy ray-curable group (b), and a photopolymerization initiation. Agent (c), and other components as needed, and the aforementioned energy ray hardening The component (a) is tricyclodecane dimethylol diacrylate, and the polymer (b) having no energy ray-curable group is selected from the group consisting of butyl acrylate, methyl acrylate, glycidyl methacrylate, and An acrylic resin obtained by copolymerizing at least one monomer in a group consisting of 2-hydroxyethyl acrylate, and the photopolymerization initiator (c) is selected from the group consisting of 2-(dimethylamino)-1 -(4-morpholinylphenyl)-2-benzyl-1-butanone and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- At least one of the group consisting of 3-yl]-, 1-(O-ethenylhydrazine), the other component of the foregoing is at least one selected from the group consisting of a filler, a coupling agent, and a coloring agent. The content of the energy ray-curable component (a) may be 18% by mass to 20% by mass based on the total mass of the film for forming a protective film; the content of the polymer (b) having no energy ray-curable group The total mass of the film for forming a protective film may be 20% by mass to 23% by mass; and the content of the photopolymerization initiator (c) may be 0.5% by mass based on the total mass of the film for forming a protective film. To 0.7% by mass; The content of said other component relative to the total mass of the protective film formation film may also be 56 mass% to 59 mass%.

[Examples]

Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited by the examples shown below.

The components for producing a composition for forming a protective film are shown below.

. Energy line hardening component

(a2)-1: tricyclodecane dihydroxymethyl diacrylate (Nippon Chemical Co., Ltd. "KAYARAD R-684", a bifunctional ultraviolet curable compound, molecular weight 304).

. Polymer without energy line hardening group

(b)-1: butyl acrylate (hereinafter abbreviated as "BA") (10 parts by mass), methyl acrylate (hereinafter abbreviated as "MA") (70 parts by mass), and glycidyl methacrylate ( Hereinafter, an acrylic resin (weight average molecular weight: 300,000, which is simply referred to as "GMA") (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass) is copolymerized. Glass transfer temperature -1 ° C).

. Photopolymerization initiator

(c)-1: 2-(Dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone (Irgacure (registered trademark) 369, manufactured by BASF Corporation) ).

(c)-2: Ethylketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) (Irgacure (registered trademark) OXE02" manufactured by BASF Corporation).

. Filler

(d)-1: cerium oxide filler (melted quartz filler, average particle diameter 8 μm).

. Coupler

(e)-1: 3-methacryloxypropyltrimethoxydecane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., decane coupling agent).

. Colorant

(g)-1: 32 parts by mass of a phthalocyanine-based blue pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone-based yellow pigment (Pigment Yellow 139), and a lanthanide red pigment (Pigment Red) 177) 50 parts by mass for mixing A pigment obtained by pigmenting the total amount of the above three kinds of dyes/the amount of styrene acrylic resin = 1/3 (mass ratio).

[Example 1]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

The energy ray curable component (a2)-1, the polymer (b)-1, the photopolymerization initiator (c)-1, the photopolymerization initiator (c)-2, the filler (d)-1, The coupling agent (e)-1 and the coloring agent (g)-1 are dissolved or dispersed in methyl ethyl ketone so that the content (solid content, mass part) is a value shown in Table 1 The mixture was stirred at 23 ° C to prepare a protective film-forming composition (IV-1) having a solid content concentration of 50% by mass. In addition, when the column containing the component in Table 1 is described as "-", it means that the protective film-forming composition (IV-1) does not contain the component.

(Manufacture of adhesive composition (I-4))

A non-energy-curable adhesive composition (I-4) having a solid content concentration of 30% by mass, wherein the adhesive composition (I-4) contains an acrylic polymer (100 parts by mass, a solid content) And a trifunctional phthalic diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content component), and further contains methyl ethyl ketone as a solvent. The acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass). Weight average molecule The amount is 600,000.

(Support for the manufacture of tablets)

The release treatment surface of the release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to a release treatment on a single side of a film made of polyethylene terephthalate, was coated with the above-mentioned obtained The adhesive composition (I-4) was dried by heating at 120 ° C for 2 minutes to form a non-energy-curable adhesive layer having a thickness of 10 μm.

Then, a polypropylene film (Young's modulus (400 MPa), thickness: 80 μm) adhered to the exposed surface of the adhesive layer is provided, and the adhesive layer is provided on one surface of the substrate. Support slice (10)-1.

(Manufacture of composite sheet for forming a protective film)

The release-treated surface of the release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to a release treatment on a single side of a polyethylene terephthalate film by a polyphthalic acid treatment, was coated by a knife The protective film-forming composition (IV-1) obtained above was applied to a cloth machine and dried at 100 ° C for 2 minutes to prepare a film (13)-1 for protective film formation having an energy ray curability of 25 μm.

Next, the release film is removed from the adhesive layer in the support sheet (10)-1 obtained above, and the exposed surface of the protective film formation film (13)-1 obtained by adhering to the exposed surface of the adhesive layer is bonded to the exposed surface of the adhesive layer. In the surface, the substrate, the adhesive layer, the protective film forming film (13)-1, and the release film are sequentially laminated in the thickness direction of these layers. A composite sheet for forming a protective film. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of composite sheet for forming a protective film>

(Adhesion between the film for forming a protective film and the support sheet)

The composite sheet for forming a protective film obtained as described above is cut into a size of 25 mm × 140 mm, and the release film is removed from the composite sheet for forming a protective film to expose one surface of the film for protective film formation (13)-1. Audition. On the other hand, a test piece of a double-sided adhesive tape was attached to the surface of a SUS (stainless steel) support plate (70 mm × 150 mm). Then, using the laminating machine ("LAMIPACKER LPD3214" manufactured by Fuji Co., Ltd.), the exposed surface of the film (13)-1 for protective film formation of the pre-hardened test piece is attached to the double-sided adhesive tape on the support plate. The support plate is attached to the pre-hardened test piece via a double-sided adhesive tape.

The tensile test was carried out using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation) under the conditions of a peeling angle of 180°, a measuring temperature of 23 ° C, and a tensile speed of 300 mm/min. The support sheet (10)-1 (the laminate of the adhesive layer before the curing and the substrate) was peeled off from the film for protective film formation (13)-1, and the load (peeling force) at this time was measured to form a protective film. The adhesion between the film (13)-1 and the support sheet (10)-1. Further, as the measured value of the load, a value obtained by peeling the support sheet (10)-1 over a length of 100 mm was used, and the first peeling was performed immediately after the length of 10 mm and the final peeling was just 10 mm. each Self-measured values are excluded from the effective value. The results are shown in Table 2.

(Tensile modulus of film for forming a protective film)

The tensile modulus (Young's rate) of the film for protective film formation (13)-1 was evaluated in the following manner.

In other words, a thickness of 50 μm was formed by laminating two sheets of a film for forming a protective film (thickness: 25 μm), and the sample was subjected to a tensile test (tensile speed: 50 mm/min) in a size of 15 mm × 100 mm, according to The tensile modulus of the film for protective film formation (13)-1 was calculated from the slope of the stress-strain line at the initial stage of stretching.

The film (13)-1 for protective film formation obtained above was cut off to prepare a test piece.

Next, the tensile modulus (Young's modulus) of the test piece at 23 ° C was measured in accordance with JIS K7161:1994. At this time, the width of the test piece was set to 15 mm, the distance between the jigs was set to 10 mm, and the stretching speed was set to 50 mm/min.

The evaluation results are shown in Table 2.

(adhesion between the protective film and the support sheet)

The test piece before hardening was produced in the same manner as in the measurement of the adhesive force of the test piece before hardening described above, and the test piece before hardening was attached to a support plate made of SUS via a double-sided adhesive tape.

Then, an ultraviolet irradiation apparatus ("RAD2000m/8" manufactured by Lintec Co., Ltd.) was used to irradiate the test specimen with ultraviolet rays under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² to thereby form a film for forming a protective film ( 13)-1 hardening, obtaining a test piece after hardening.

Then, the cured test piece was measured between the protective film obtained by curing the film for protective film (13)-1 and the support sheet (10)-1 by the same method as in the case of the test piece before curing described above. Adhesion. The results are shown in Table 2.

<Tensile modulus of protective film>

The film (13)-1 for protective film formation obtained above was cut off to prepare a test piece.

Then, the test piece was irradiated with ultraviolet rays under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.) to thereby form a film for forming a protective film (13). )-1 hardens to obtain a protective film test piece.

Next, the tensile modulus (Young's modulus) of the protective film test piece at 23 ° C was measured in accordance with JIS K7161:1994. At this time, the width at the time of measurement of the protective film test piece was set to 15 mm, the distance between the jigs was set to 10 mm, and the tensile speed was set to 50 mm/min.

The evaluation results are shown in Table 2.

(cutting evaluation)

The protective film forming composite sheet obtained as described above was attached to a #2000 polished surface of a 8 Å wafer (thickness: 100 μm) by the protective film forming film (13)-1 of the protective film forming composite sheet. And fixing the piece to the ring frame , let stand for 30 minutes.

Next, an ultraviolet ray irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.) was used to provide an outer diameter of 12 吋 inner diameter 8 in contact with the support sheet (10)-1 between the UV light source and the support sheet (10)-1. A shielding sheet made of SUS having a ring shape and a thickness of 10 mm is used to form a composite sheet for forming a protective film from the side of the support sheet (10)-1 via the shielding plate under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² . By irradiating the ultraviolet ray, the film for protective film formation (13)-1 of the attachment region of the semiconductor wafer other than the region in the vicinity of the peripheral portion of the film (13)-1 for protective film formation is cured to become a protective film. .

Next, using a dicing blade, the ruthenium wafer was cut together with the protective film to be singulated, and a 3 mm × 3 mm ruthenium wafer was obtained.

Next, using a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.), 20 wafers with a protective film were picked up under an extension of 3 mm.

In this case, if it can be picked up without error, it is judged as "A", and if there is a mistake, it is judged as "B", and the pickup suitability is evaluated. The results are shown in Table 2. In addition, the measurement results of the slit width after the extension at this time are shown in Table 2.

[Embodiment 2]

<Manufacture and Evaluation of Protective Film Forming Composite Sheet>

(Support for the manufacture of tablets)

The above-mentioned peeling-treated surface of a release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to a release treatment on a single side of a polyethylene terephthalate film by a polyphthalic acid treatment was applied as described above. Adhesive The agent composition (I-4) was dried by heating at 120 ° C for 2 minutes to form a non-energy-curable adhesive layer having a thickness of 10 μm.

Next, a light-shielding layer made of a printed layer was provided on one surface of a polypropylene-based film (Young's ratio (400 MPa), thickness: 80 μm) as a substrate, and the printed layer had an outer diameter of 12 吋 and an inner diameter of 8 Å. It has a ring shape, a thickness of 2 μm, and is light-shielding.

Then, the other surface of the substrate obtained above is bonded to the exposed surface of the adhesive layer obtained above, thereby obtaining a support sheet (10) having the above-mentioned adhesive layer on the other surface of the substrate- 2.

(Manufacture and evaluation of composite sheet for forming a protective film)

A sheet for forming a protective film was produced in the same manner as in Example 1 except that the support sheet (10)-2 obtained above was used.

In addition, the support sheet (10)-2 was used instead of the support sheet (10)-1, and a composite sheet for forming a protective film was produced in the same manner as in Example 1 except for the above. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

Evaluation results of the adhesion between the film for forming a protective film and the support sheet, the tensile modulus of the film for forming a protective film, the adhesion between the protective film and the support sheet, and the tensile modulus of the protective film, and Example 1 the same.

(cutting evaluation)

The protective film forming composite sheet obtained as described above was attached to a #2000 polished surface of a 8 Å wafer (thickness: 100 μm) by the protective film forming film (13)-1 of the protective film forming composite sheet. And fixing the piece to the ring frame , let stand for 30 minutes.

Next, using a UV irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.), a light-shielding layer self-supporting sheet (10) composed of a printed layer was formed under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² . The film for protective film formation of the attachment region of the semiconductor wafer other than the region in the vicinity of the peripheral portion of the film (13)-1 in the protective film forming film (13)-1 is irradiated with ultraviolet rays on the first side. )-1 hardens and becomes a protective film.

Next, using a dicing blade, the ruthenium wafer was cut together with the protective film to be singulated, and a 3 mm × 3 mm ruthenium wafer was obtained.

Next, using a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.), 20 wafers with a protective film were picked up under an extension of 3 mm.

In this case, if it can be picked up without error, it is judged as "A", and if there is a mistake, it is judged as "B", and the pickup suitability is evaluated. The results are shown in Table 2. In addition, the measurement results of the slit width after the extension at this time are shown in Table 2.

[Example 3]

<Manufacture and Evaluation of Composite Sheet for Forming Protective Film>

(Manufacture of composite sheet for forming a protective film)

A polypropylene film (thickness: 80 μm) used as a substrate in Example 1 was replaced with a polyvinyl chloride film (Young's ratio (280 MPa), thickness: 80 μm), and the same as Example 1 except for the above. In the way, support piece (10)-3 is produced.

And, the support piece (10)-3 is used instead of the support piece (10)-1, except for this side. A composite sheet for forming a protective film was produced in the same manner as in Example 1 except for the surface. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

Evaluation results of the adhesion between the film for forming a protective film and the support sheet, the tensile modulus of the film for forming a protective film, the adhesion between the protective film and the support sheet, and the tensile modulus of the protective film, and Example 1 the same.

(cutting evaluation)

The support sheet (10)-1 used in Example 1 was replaced with the support sheet (10)-3, and in addition to this, the cut evaluation was performed in the same manner as in Example 1.

The results are shown in Table 2.

[Example 4]

<Manufacture and Evaluation of Composite Sheet for Forming Protective Film>

(Manufacture of composite sheet for forming a protective film)

A polypropylene film (thickness: 80 μm) used as a substrate in Example 1 was replaced with a polyvinyl chloride film (Young's ratio (280 MPa), thickness: 80 μm), and the same as Example 2 except for this. Way, make support piece (10)-4.

In addition, the support sheet (10)-4 was used instead of the support sheet (10)-1, and a composite sheet for forming a protective film was produced in the same manner as in Example 1 except for the above. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

Adhesion between the film for forming a protective film and the support sheet, tensile modulus of the film for forming a protective film, adhesion between the protective film and the support sheet, and protection The evaluation results of the tensile modulus of the film were the same as in Example 1.

(cutting evaluation)

The support sheet (10)-1 used in Example 1 was replaced with the support sheet (10)-4, and in addition to this, the cut evaluation was performed in the same manner as in Example 1.

The results are shown in Table 2.

[Comparative Example 1]

<Manufacture and Evaluation of Composite Sheet for Forming Protective Film>

(Manufacture of composite sheet for forming a protective film)

The support sheet (10)-1 was produced in the same manner as in the first embodiment.

Evaluation results of the adhesion between the film for forming a protective film and the support sheet, the tensile modulus of the film for forming a protective film, the adhesion between the protective film and the support sheet, and the tensile modulus of the protective film, and Example 1 the same.

(cutting evaluation)

In the same manner as in the first embodiment, the entire composite sheet for forming a protective film was irradiated with ultraviolet rays from the side of the support sheet (10)-1, except that the shield plate made of SUS used in the first embodiment was not used. Perform the cutting evaluation.

The results are shown in Table 2.

[Comparative Example 2]

<Manufacture and Evaluation of Composite Sheet for Forming Protective Film>

(Manufacture of composite sheet for forming a protective film)

The support sheet (10)-3 was produced in the same manner as in the third embodiment.

Evaluation results of the adhesion between the film for forming a protective film and the support sheet, the tensile modulus of the film for forming a protective film, the adhesion between the protective film and the support sheet, and the tensile modulus of the protective film, and Example 1 the same.

(cutting evaluation)

In the same manner as in the third embodiment, the entire composite sheet for forming a protective film is irradiated with ultraviolet rays from the side of the support sheet (10)-3, except that the shield plate made of SUS used in the first embodiment is not used. Perform the cutting evaluation.

The results are shown in Table 2.

According to the results of the first embodiment to the fourth embodiment, it is clear that when the semiconductor wafer is diced by irradiating the energy line to the portion of the semiconductor wafer other than the region near the peripheral portion of the film for forming a protective film. Can improve picking. It is estimated that the portion of the adhesion region of the semiconductor wafer in the film for forming a protective film is irradiated with an energy ray, and a region where the film for protective film formation is not cured is present in a region in the vicinity of the peripheral portion of the support sheet, thereby extending the laminate. In this case, the effect of the stretching is spread over the region where the semiconductor wafer is adhered to the film for forming a protective film, and the slit width can be expanded more favorably, whereby the pickup property can be improved.

On the other hand, in Comparative Example 1 to Comparative Example 2, it is estimated that the entire protective film forming composite sheet is irradiated with ultraviolet rays from the side of the support sheet (10)-1, and the protective film forming film contains the attached region of the semiconductor wafer. When the laminate is extended as a whole, the hard protective film in the region of the protective film forming film in which the outer periphery of the semiconductor wafer is not attached is an obstacle, and the effect of the extension does not spread well over the central portion. The attachment area of the semiconductor wafer causes poor pickup.

(industry availability)

The invention can be used to fabricate semiconductor devices.

1A‧‧‧Composite film for protective film formation

10‧‧‧Support tablets

10a‧‧‧ (supported) surface

11‧‧‧Substrate

11a‧‧‧ (substrate) surface

12‧‧‧Adhesive layer

12a‧‧‧ (adhesive layer) surface

13‧‧‧film for protective film formation

13a‧‧‧ (film for protective film formation)

15‧‧‧Release film

16‧‧‧Layer layer for fixtures

16a‧‧‧ (adhesive layer for the fixture) surface

24‧‧‧ shading layer

Claims (7)

A composite sheet for forming a protective film is formed by a film for forming a protective film having an energy ray-curable property on a support sheet, and the support sheet has a light-shielding layer in a region in the vicinity of the peripheral portion. The composite sheet for forming a protective film according to claim 1, wherein the light shielding layer is composed of a printed layer. A method for producing a semiconductor wafer with a protective film, comprising: the semiconductor wafer and the protection in a laminate of a protective film forming film and a semiconductor wafer which are provided with a support sheet, an energy ray-curable layer, and a semiconductor wafer; The film for film formation is diced, and an energy ray is applied to the affixed portion of the film for forming a protective film, except for a region in the vicinity of the peripheral portion, to form a protective film on the support sheet. a semiconductor wafer; and picking up the aforementioned semiconductor wafer with a protective film. A method for producing a semiconductor wafer with a protective film, comprising: a film for forming a protective film in a laminate for a protective film for forming a support sheet or an energy ray-curable film and a semiconductor wafer; Irradiating the energy line with the attachment region of the semiconductor wafer except for the region near the peripheral portion; after irradiating the energy line, cutting the semiconductor wafer to form a semiconductor wafer with a protective film on the support sheet; The semiconductor wafer with the protective film is picked up. The method for producing a semiconductor wafer with a protective film according to claim 3 or 4, wherein the support sheet has a light shielding layer in a region in the vicinity of the peripheral portion. The method for producing a semiconductor wafer with a protective film according to claim 3 or 4, wherein a portion of the film for forming a protective film other than a region near a peripheral portion of the protective film is partially interposed The shielding plate illuminates the energy line. A method of manufacturing a semiconductor device, comprising: attaching a semiconductor wafer with a protective film obtained by the method for producing a semiconductor wafer with a protective film according to any one of claims 3 to 6 to a substrate.