TW202348756A - Protective film-forming film, composite sheet for forming protective film, method of manufacturing semiconductor device, and use of protective film-forming film having desirable storage elastic modulus for a test piece formed by multiple pieces of the protective films - Google Patents

Abstract

The present invention provides a protective film-forming film, which is a thermosetting protective film-forming film, wherein a first test piece with a width of 4 mm, which is a laminate of a plurality of the protective film-forming films, has a storage elastic modulus E' measured at a temperature range of 23 DEG C to 70 DEG C, the minimum value E'(1) being 45 MPa or less, and the maximum value E'(2) being 200 MPa or more. For a cured product obtained by thermally curing the laminate formed by multiple pieces of the protective films as a second test piece with a width of 5 mm, when the storage elastic modulus E is measured under the same conditions, the minimum value E'(3) is 500 MPa or more.

Description

Protective film forming film, protective film forming composite sheet, manufacturing method of semiconductor device, and use of protective film forming film

The present invention relates to a protective film-forming film, a protective film-forming composite sheet, a manufacturing method of a semiconductor device, and the use of a protective film-forming film. This case claims priority based on Special Application No. 2022-055423 filed in Japan on March 30, 2022, and the content is quoted here.

Some semiconductor wafers have circuits formed on one side (circuit side) and have protruding electrodes such as bumps on this side (circuit side). This semiconductor wafer is divided into semiconductor wafers, and is mounted on the circuit board by connecting its protruding electrodes to connection pads on the circuit board. In such semiconductor wafers and semiconductor wafers, in order to prevent damage such as cracks from occurring, a protective film may be used to protect the surface opposite to the circuit surface (inner surface).

In order to form such a protective film, a protective film-forming film for forming a protective film is attached to the inner surface of the semiconductor wafer. The protective film-forming film may be laminated on a support sheet for supporting the protective film-forming film and may be used in the form of a protective film-forming composite sheet, or may be used without being laminated on the support sheet. Next, the semiconductor wafer usually having a protective film-forming film on its inner surface (a semiconductor wafer with a protective film-forming film) is processed through various subsequent steps into a semiconductor wafer having a protective film on its inner surface (a semiconductor wafer with a protective film). semiconductor wafer). This semiconductor wafer with a protective film is picked up and mounted on the circuit surface of the substrate to form a semiconductor device. The protective film-forming film system forms a protective film by curing, for example.

On the other hand, the protective film-forming film is sometimes used in such a way that the protective film is not formed until the semiconductor wafer is mounted on the circuit surface of the substrate, but is formed by curing after the semiconductor wafer is mounted on the circuit surface of the substrate. Protective film. In this case, until the semiconductor wafer is mounted on the circuit surface of the substrate, the semiconductor wafer or the inner surface of the semiconductor wafer is in a state where a protective film-forming film that is softer than the protective film is attached. This may sometimes occur. cause problems.

For example, when picking up a semiconductor wafer with a protective film-forming film that has a semiconductor wafer and a protective film-forming film provided on the inner surface of the semiconductor wafer, the semiconductor wafer with the protective film-forming film has When the protective film is formed, the side end of the film will be pushed up with a pin through a cutting sheet or other sheet. At this time, the protruding mark of the pin may remain on the protective film forming film, thereby damaging the appearance of the protective film forming film. For example, in a semiconductor wafer with a protective film forming film, laser printing may be performed by irradiating a surface of the protective film forming film opposite to the semiconductor wafer side in some cases. In this case, if the printed protective film is hardened, the printing may become unclear or disappear.

Therefore, there is a desire to solve these problems, but for this purpose, the protective film-forming film must have good adhesion properties to the semiconductor wafer and protective suitability to form a protective film with high protective performance.

In this regard, a method of manufacturing a semiconductor device including a step of performing laser printing on an uncured protective film-forming film, and a protective film-forming film used in this method of manufacturing a semiconductor device are disclosed (see Patent Document 1 to Patent Document 1). Document 2). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2018-81953. [Patent Document 2] Japanese Patent Application Publication No. 2013-149737.

[Problem to be solved by the invention]

However, it is not certain whether the protective film-forming films disclosed in Patent Documents 1 to 2 can solve all the above-mentioned problems, that is, whether they can form a protective film that can suppress the lifting traces of the remaining pins and maintain the state of the protective film. It can clearly maintain the printing produced by laser light irradiation, has good adhesion to semiconductor wafers, and has high protection performance.

An object of the present invention is to provide a thermosetting protective film-forming film for forming a protective film on the inner surface of a semiconductor wafer, that is, a protective film-forming film provided on the inner surface of a semiconductor wafer with a protective film-forming film When the semiconductor wafer is handled in an unhardened state until it is mounted on the circuit surface of the substrate, when the semiconductor wafer with the protective film-forming film is picked up with a pin, protection can be suppressed. The film-forming film has traces of pin lifting remaining; when the protective film-forming film is laser printed and then thermally hardened to form a protective film, it is possible to form a state where the printing is clearly maintained and the adhesion to the semiconductor wafer is achieved A good protective film with high protective performance. Another object of the present invention is to provide a protective film-forming composite sheet including the protective film-forming film, and to provide a method of manufacturing a semiconductor device using the protective film-forming film or the protective film-forming composite sheet. [Means used to solve problems]

In order to solve the aforementioned problems, the present invention adopts the following configuration. [1]. A protective film-forming film that is thermosetting, and a first test piece with a width of 4 mm, which is a laminate of a plurality of the aforementioned protective film-forming films, is held at two places with an interval of 20 mm, and is stretched In the stretching mode, under the conditions of constant temperature rise with a frequency of 11Hz and a heating rate of 3°C/min, the first test piece is heated from −20°C to 150°C while the first test piece is stored. When the elastic modulus E' is measured, the minimum value E'(1) of the aforementioned storage elastic modulus E' in the temperature range of 23°C to 70°C is 45MPa or less, and in the temperature range of 23°C to 70°C The maximum value E'(2) of the storage elastic modulus E' in the temperature range is 200 MPa or more; and a cured product obtained by thermally curing a plurality of laminates of the protective film-forming film and having a width of 5 mm The two test pieces are held in two places with a distance of 20mm apart, and the second test piece is heated from −60°C in the tensile mode at a constant temperature with a frequency of 11Hz and a heating rate of 3°C/min. When the temperature is raised to 350°C and the storage elastic modulus E' of the second test piece is measured, the minimum value E' of the storage elastic modulus E' in the temperature range of 23°C to 70°C ( 3) is above 500MPa. [2]. The protective film-forming film according to [1], wherein the protective film-forming film contains a hardening accelerator (C). [3]. The protective film-forming film according to [1] or [2], wherein the protective film-forming film is a single layer. [4]. A composite sheet for forming a protective film, including a support sheet; and a protective film-forming film disposed on one surface of the support sheet; wherein the protective film-forming film is any one of [1] to [3] The protective film forming film described in this item.

[5]. A method of manufacturing a semiconductor device, the manufacturing method having the following steps: attaching a protective film as described in any one of [1] to [3] to form one side of the film or as described in [4] The exposed surface of the protective film-forming film in the composite sheet for protective film formation is attached to the inner surface of the semiconductor wafer; the printing step is after the aforementioned attaching step, when the aforementioned composite sheet for protective film formation is used , perform laser printing on the surface of the protective film-forming film on the side of the supporting sheet in the protective film-forming composite sheet, and when using the protective film-forming film that does not constitute the protective film-forming composite sheet, The other side of the protective film forming film is subjected to laser printing; the processing step is after the printing step, when the composite sheet for forming a protective film is used, on the supporting sheet in the composite sheet for forming a protective film , the aforementioned semiconductor wafer is divided into semiconductor wafers, and the aforementioned protective film forming film is cut along the divisions of the aforementioned semiconductor wafer, and when the aforementioned protective film forming film is used without forming the aforementioned protective film forming composite sheet, After attaching a dicing piece to the other side of the protective film-forming film, the semiconductor wafer is divided into semiconductor wafers on the dicing piece, and the protective film-forming film is cut along the division points of the semiconductor wafer. To manufacture a semiconductor wafer with a protective film-forming film, it is provided with the aforementioned semiconductor wafer and the cut-off aforementioned protective film-forming film provided on the inner surface of the aforementioned semiconductor wafer; the picking-up step is to pick up the aforementioned protective film-forming film after the aforementioned processing step. The semiconductor wafer with the protective film forming film is pulled away from the aforementioned cutting piece or the supporting piece and picked up; the bonding step is after the aforementioned picking up step, by removing the protruding electrodes in the aforementioned semiconductor wafer with the protective film forming film that has been picked up Flip-chip bonding to the circuit surface of the substrate, so that the semiconductor chip with the protective film-forming film is bonded to the circuit surface; and the thermal hardening step is after the aforementioned bonding step, by making the aforementioned protective film-forming film The protective film-forming film in the semiconductor wafer is thermally cured to form a protective film. [6]. The use of a protective film-forming film that is attached to the inner surface of a semiconductor wafer on the opposite side to the circuit surface to form protection on the inner surface of the semiconductor wafer obtained by dividing the aforementioned semiconductor wafer. Film; the aforementioned protective film-forming film is the protective film-forming film described in any one of [1] to [3]. [Invention effect]

According to the present invention, it is possible to provide a thermosetting protective film-forming film for forming a protective film on the inner surface of a semiconductor wafer, which is a thermosetting protective film-forming film provided on the inner surface of a semiconductor wafer. When the semiconductor wafer is handled in an uncured state until it is mounted on the circuit surface of the substrate, when the semiconductor wafer with the protective film-forming film attached is lifted up with a pin and picked up, the protective film can be suppressed. The formed film has traces of pin lifting remaining, and when the protective film forming film is laser printed and then thermally hardened to form a protective film, it can maintain the printing in a clear manner and have good adhesion to the semiconductor wafer. A good protective film with high protective performance. Furthermore, according to the present invention, it is possible to provide a protective film-forming composite sheet including the protective film-forming film, and to provide a semiconductor device manufacturing method using the protective film-forming film or the protective film-forming composite sheet.

◇Protective film forming film According to one embodiment of the present invention, the protective film-forming film is a thermosetting protective film-forming film. A first test piece with a width of 4 mm, which is a laminate of a plurality of the protective film-forming films, is separated by two 20 mm intervals. The first test piece was heated from −20°C to 150°C in the tensile mode at a constant rate of temperature rise with a frequency of 11 Hz and a heating rate of 3°C/min. When the storage elastic modulus E' of the first test piece is measured, the minimum value E'(1) (sometimes referred to as "E'(1)" in this specification) of the storage elastic modulus E' is 45 MPa or less, The maximum value E'(2) of the aforementioned storage elastic modulus E' (sometimes referred to as "E'(2)" in this specification) is 200 MPa or more; obtained by thermally hardening a laminate of a plurality of the aforementioned protective film-forming films. The hardened material and the second test piece with a width of 5mm were held in two places with an interval of 20mm, and under the conditions of constant temperature rise with a frequency of 11Hz and a heating rate of 3°C/min in the tensile mode, one side was When the storage elastic modulus E' of the second test piece is measured while the temperature of the second test piece is raised from −60°C to 350°C, the minimum value E' of the storage elastic modulus E'(3) (In this specification, it may be abbreviated as "E'(3)") is 500MPa or more. The protective film-forming film of this embodiment can be laminated with a support sheet to form a protective film-forming composite sheet, as will be described later, for example.

By using the protective film-forming film of this embodiment or the protective film-forming composite sheet provided with the protective film-forming film, it is possible to produce a protective film-forming film including a semiconductor wafer and a protective film-forming film provided on the inner surface of the semiconductor wafer. A semiconductor wafer with a protective film forming film is formed. In addition, a semiconductor wafer with a protective film provided with a semiconductor wafer and a protective film provided on an inner surface of the semiconductor wafer can be manufactured by using the semiconductor wafer provided with the protective film-forming film. In addition, a semiconductor device can be manufactured by using a semiconductor wafer with a protective film.

The protective film-forming film of this embodiment is suitable for use as a manufacturing method of a semiconductor device. It is not used until the semiconductor wafer with the protective film-forming film is flip-chip connected to the circuit surface of the substrate. The protective film forming film is thermally hardened (in other words, the protective film is not formed), and thermal hardening (protective film formation) is performed only in the reflow step after flip-chip connection.

A circuit is formed on one surface of the semiconductor wafer. In this specification, the surface of the semiconductor wafer on which the circuit is formed is called a "circuit surface". In addition, the surface of the semiconductor wafer opposite to the circuit surface is called the "inner surface". The semiconductor wafer is divided into semiconductor wafers by means such as dicing. In this specification, as in the case of a semiconductor wafer, the surface of the semiconductor wafer on which the circuit is formed is called the "circuit surface" and the surface of the semiconductor wafer opposite to the circuit surface is called the "inner surface". It is preferable that the circuit surface of the semiconductor wafer and the circuit surface of the semiconductor chip are both provided with protruding electrodes such as bumps and pillars. The protruding electrode is preferably made of solder.

In addition, a semiconductor device can be manufactured by using the aforementioned semiconductor wafer with a protective film. In this specification, an example of a "semiconductor device" is a semiconductor device formed by placing a semiconductor wafer with a protective film on the protruding electrodes on the circuit surface of the semiconductor wafer and flip-chip connecting it to the connection pads on the circuit substrate. .

The protective film-forming film of this embodiment has thermosetting properties, and is used as a protective film by utilizing its thermosetting properties.

By heating the normal-temperature protective film to a temperature exceeding normal temperature and then cooling it to normal temperature, the heated/cooled protective film is formed as a protective film at the same temperature. When comparing the hardness with the hardness of the protective film-forming film before heating, when the protective film-forming film after heating/cooling is relatively hard, the protective film-forming film is thermosetting.

The protective film-forming film of this embodiment may be composed of one layer (single layer), or may be composed of two or more layers. When the protective film-forming film is composed of multiple layers, these multiple layers may be the same as or different from each other, and the combination of these multiple layers is not particularly limited.

In this specification, it is not limited to the case where a protective film is formed into a film. The so-called "multiple layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only some of the layers may be the same", and further, The term "multiple layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

Among them, the protective film-forming film of this embodiment is preferably one layer (single layer). By forming the protective film as one layer, it is possible to highly suppress the protective film or the protective film from being peeled off from its adjacent layer during the reflow step. In addition, unlike multiple sheets of protective film-forming films, when one layer of protective film-forming film is stored, the components contained therein do not transfer between layers, so the storage stability is higher. Also, a protective film-forming film can be manufactured more easily.

＜＜E’(1)＞ The storage elastic modulus E' of the protective film-forming film before curing (unhardened) was measured by laminating and cutting out a plurality of pieces of the protective film-forming film to produce a laminated product with a width of 4 mm, and This laminate was used as a first test piece. More specifically, the first test piece was held in two places with an interval of 20 mm. In this state, the first test piece was heated at a constant speed from −20°C to Measure the storage elastic modulus E' of the first test piece at 150°C and a frequency of 11Hz. Holding the first test piece at two locations with an interval of 20 mm means that the length of the portion to be measured for the storage elastic modulus E' of the first test piece is 20 mm.

The first test piece can be held at the above two places by, for example, a known clamp or other clamping means.

The thickness of the first test piece (the aforementioned laminated material) is not particularly limited as long as it does not hinder the implementation of the aforementioned test and does not impair the measurement accuracy of the aforementioned storage elastic modulus E’. Generally, the thickness of the first test piece is preferably 190 μm to 210 μm, more preferably 195 μm to 205 μm, and particularly preferably 200 μm.

The number of protective film-forming films constituting the first test piece is not particularly limited as long as it is two or more, and can be selected arbitrarily according to the thickness of each protective film-forming film. For example, by forming a film using five protective films with a thickness of 40 μm, a first test piece with a thickness of 200 μm can be produced. In addition, by using eight protective films with a thickness of 25 μm to form a film, a first test piece with a thickness of 200 μm can be produced. However, these are only examples, and the number and thickness of the protective film-forming films used are not limited thereto.

In this embodiment, the minimum value E'(1) of the storage elastic modulus E' of the first test piece in the temperature range of 23°C to 70°C is 45 MPa or less. In this way, since the protective film-forming film has a softness above a certain level at a temperature of 23°C to 70°C, the adhesion of the protective film-forming film to the semiconductor wafer becomes good. E'(1) may be, for example, any value of 40 MPa or less, 30 MPa or less, or 15 MPa or less. The smaller E'(1) is, the better the adhesion of the protective film forming film to the semiconductor wafer is. The lower limit of E’(1) is not particularly limited. For example, from the viewpoint of easily obtaining a protective film-forming film, E'(1) may be 0.01 MPa or more. In an embodiment, E'(1) may also be any value from 0.01 MPa to 45 MPa, 0.01 MPa to 40 MPa, 0.01 MPa to 30 MPa, and 0.01 MPa to 15 MPa. However, these are only examples of E’(1).

E'(1), usually the storage elastic modulus E' of the first test piece when the temperature of the first test piece is 70°C, is suitable for temperatures around 70°C (for example, 65°C to 75°C). This is the heating temperature of the protective film forming film when attaching the protective film forming film to the semiconductor wafer (attaching temperature of the protective film forming film).

＜＜E’(2)＞ In this embodiment, the maximum value E'(2) of the storage elastic modulus E' of the first test piece in the temperature range of 23°C to 70°C is 200 MPa or more. In this way, the protective film-forming film has a hardness above a certain level at a temperature of 23°C to 70°C. As will be described later, in the process of semiconductor device manufacturing, the semiconductor wafer with the protective film-forming film is lifted up with pins. When picking up, it is possible to suppress the lifting marks of pins remaining on the protective film. Furthermore, when the protective film-forming film is laser-printed and then thermally cured to form a protective film, the printing can be clearly retained on the protective film. E'(2) may be, for example, any one of 250 MPa or more, 350 MPa or more, and 450 MPa or more. The larger E’(2) is, the higher the effect of suppressing the lifting marks of the remaining pins on the protective film and retaining the printing on the protective film in a clear manner. The upper limit of E’(2) is not particularly limited. For example, from the viewpoint of easily obtaining a protective film-forming film, E'(2) may be 800 MPa or less. In one embodiment, E'(2) may be any value from 250 MPa to 800 MPa, 350 MPa to 800 MPa, and 450 MPa to 800 MPa. However, these are only examples of E’(2).

E'(2), usually the storage elastic modulus E' of the first test piece when the temperature of the first test piece is 23°C, a temperature of about 23°C (for example, 18°C to 28° C) A temperature suitable for the protective film forming film when performing laser printing on the protective film forming film and when picking up the semiconductor wafer with the protective film forming film by lifting it with a pin.

＜＜E’(3)＞ The measurement of the storage elastic modulus E′ concerning the thermally cured product of the protective film-forming film is obtained by laminating a plurality of pieces of the protective film-forming film, cutting them out to produce a laminated product, and thermally curing the laminated product. A hardened material with a width of 5 mm was used as a second test piece and measured. More specifically, the aforementioned second test piece was held in two places with an interval of 20 mm. In this state, the second test piece was heated at a constant speed from −60°C to 350° at a heating rate of 3°C/min. C, while measuring the storage elastic modulus E' of the second test piece at a frequency of 11 Hz. Holding the second test piece at two locations with an interval of 20 mm means that the length of the portion to be measured for the storage elastic modulus E' of the second test piece is 20 mm.

The second test piece can be held at the two places in the same manner as the first test piece is held at the two places.

The thickness of the second test piece (the aforementioned hardened material) is not particularly limited as long as it does not hinder the implementation of the aforementioned test and does not impair the measurement accuracy of the aforementioned storage elastic modulus E’. Generally, the thickness of the second test piece is preferably 190 μm to 210 μm, more preferably 195 μm to 205 μm, and particularly preferably 200 μm.

The number of protective film-forming films constituting the laminate used to produce the second test piece is not particularly limited as long as it is two or more, and can be selected arbitrarily according to the thickness of each protective film-forming film. For example, by forming a film using five protective films with a thickness of 40 μm, the above-described laminate and the second test piece with a thickness of 200 μm can be produced. In addition, by forming a film using eight protective films with a thickness of 25 μm, the aforementioned laminated product and the second test piece with a thickness of 200 μm can be produced. Normally, the thickness of the laminate is the same as the thickness of the second test piece. However, these are only examples, and the number and thickness of the protective film-forming films used are not limited thereto.

In this embodiment, the minimum value E'(3) of the storage elastic modulus E' of the second test piece in the temperature range of 23°C to 70°C is 500 MPa or more. In this way, the thermosetting material formed by the protective film (in other words, the protective film) has a hardness above a certain level at any temperature from 23°C to 70°C, and the protective film has a high degree of protective performance. E'(3) may be, for example, any value of 2,000 MPa or more, 3,500 MPa or more, 5,000 MPa or more, and 6,500 MPa or more. The larger E’(3) is, the better the protective performance of the protective film can be improved. The upper limit of E’(3) is not particularly limited. For example, from the viewpoint of easily obtaining a protective film, E'(3) may be 10,000 MPa or less. In one embodiment, E'(3) may be, for example, any one of 500MPa to 10000MPa, 2000MPa to 10000MPa, 3500MPa to 10000MPa, 5000MPa to 10000MPa, and 6500MPa to 10000MPa. However, these are only examples of E’(3).

E'(3) is usually the storage elastic modulus E' of the second test piece when the temperature of the second test piece is 23°C, a temperature of about 23°C (for example, 18°C to 28°C ) is usually the temperature at which items with protective films such as semiconductor chips with protective films are frequently operated.

In this embodiment, it is preferable that E’(1) and E’(2) of the first test piece and E’(3) of the second test piece are within any of the aforementioned numerical ranges. For example, as an example of a preferable protective film-forming film, there can be exemplified a protective film-forming film in which E'(1) is any one of 0.01MPa to 45MPa, 0.01MPa to 40MPa, 0.01MPa to 30MPa, and 0.01MPa to 15MPa. Within the range, E'(2) is any one of 250MPa to 800MPa, 350MPa to 800MPa, and 450MPa to 800MPa, and E'(3) is 500MPa to 10000MPa, 2000MPa to 10000MPa, 3500MPa to 10000MPa, 5000MPa to 10000MPa , and within any range from 6500 MPa to 10000MPa.

The storage elastic modulus E' of the first test piece mainly E'(1) and E'(2), and the storage elastic modulus E' of the second test piece mainly E'(3) are both This can be adjusted by adjusting the types and contents of the components contained in the protective film-forming film. For example, when the protective film-forming film contains the polymer component (A) described below, by adjusting the type and content of the structural units of the polymer component (A), the first test piece and the second test piece can be more easily adjusted. 2. Storage elastic modulus E' of the test piece. More specifically, for example, by using a polymer component (A), especially an acrylic resin described below as the polymer component (A), and by adjusting the glass transition temperature (Tg) of the acrylic resin, the first temperature can be adjusted more easily. Storage elastic modulus E' of the test piece and the second test piece. As the polymer component (A), there is a tendency that by selecting a polymer component (A) with a higher Tg, E'(1) can be made smaller more easily and E'(2) and E'( 3) Get bigger. For example, when the protective film-forming film contains a filler (D) described below, by adjusting the content of the filler (D) in the protective film-forming film, the relationship between the first test piece and the second test piece can be more easily adjusted. Store the elastic modulus E' (especially E'(1), E'(2) and E'(3)).

The thickness of the protective film-forming film is not particularly limited. The thickness of the protective film-forming film is preferably 50 μm or less. For example, it may be any value of 40 μm or less and 30 μm or less. By setting the thickness of the protective film-forming film to be less than the aforementioned upper limit, excessive thickness of the protective film-forming film can be avoided. On the other hand, from the viewpoint of being able to form a protective film with higher protective performance, the thickness of the protective film-forming film is preferably 5 μm or more. In one embodiment, the thickness of the protective film forming film may be, for example, any one of 5 μm to 50 μm, 5 μm to 40 μm, and 5 μm to 30 μm. However, these are only examples of the thickness of the protective film forming film.

In this specification, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. For example, the thickness of the protective film-forming film composed of a plurality of sheets means the total thickness of all the layers constituting the protective film-forming film.

In this specification, it is not limited to the case where a protective film is formed into a film. Unless otherwise specified, the "thickness" is the average thickness measured at five randomly selected places on the object, and uses the constant pressure thickness in accordance with JIS K7130. Measuring instrument can obtain the thickness.

The curing conditions when the protective film-forming film is attached to a target portion of a semiconductor wafer and thermally cured to form a protective film are not particularly limited as long as the degree of curing is such that the protective film can fully exert its functions. It can be appropriately selected according to the type of protective film forming film.

For example, the heating temperature during thermal hardening of the protective film-forming film may be in any range of 100°C to 200°C, 120°C to 195°C, and 140°C to 190°C. The heating time during thermal hardening can be appropriately set taking into account the heating temperature. For example, it can be in any range from 3 minutes to 5 hours, from 3 minutes to 1 hour, and from 3 minutes to 30 minutes.

The protective film-forming film of this embodiment is attached to the inner surface of the semiconductor wafer on the opposite side to the circuit surface, and forms a protective film on the inner surface of the semiconductor wafer obtained by dividing the semiconductor wafer. The protective film-forming film of this embodiment has good adhesion to the aforementioned inner surface of the semiconductor wafer, and has high protective performance for the semiconductor wafer. The protective film forming film of this embodiment is further suitable for being attached to a semiconductor wafer and then printing on the surface opposite to the side of the semiconductor wafer by irradiating it with laser light. This kind of printing will remain clearly on the protective film even when the protective film is formed by thermal hardening of the protective film-forming film. The protective film-forming film of this embodiment is further suitable for picking up the semiconductor wafer having the protective film-forming film (that is, with Protective film forming film for semiconductor wafer). When picking up in this way, it is possible to suppress the protruding marks of the remaining pins in the protective film-forming film provided on the inner surface of the semiconductor wafer.

＜＜Composition for protective film formation＞＞ The aforementioned protective film-forming film can be formed by using a protective film-forming composition (more specifically, a thermosetting protective film-forming composition) containing its constituent material. For example, the protective film-forming film is formed by applying a protective film-forming composition to the surface to be formed and drying it as necessary. The ratio of the contents of components that do not vaporize at normal temperature in the protective film-forming composition to each other is generally the same as the ratio of the contents of the aforementioned components to each other in the protective film-forming film. In this specification, "normal temperature" refers to a temperature that is not particularly cold or hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C.

The protective film-forming film may have energy ray curability in addition to thermosetting properties.

In this specification, the so-called "energy line" means an electromagnetic wave or a charged particle beam with energy quanta. Examples thereof include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In this specification, "energy ray hardenability" means the property of being hardened by irradiation with energy rays, and "non-energy ray hardenability" means the property of not being hardened even if energy rays are irradiated.

In the protective film-forming film, the ratio of the total content of one or more of the components described below in the protective film-forming film to the total mass of the protective film-forming film does not exceed 100 mass %. Similarly, in the protective film-forming composition, the ratio of the total content of one or more of the following components in the protective film-forming composition to the total mass of the protective film-forming composition shall not exceed 100 mass %.

Coating the composition for forming a protective film can be carried out by a known method, for example, air knife coater, blade coater, rod coater, gravure coater, roll coater, roller knife coater, curtain Methods using various coaters, such as coaters, die coaters, knife coaters, screen coaters, Mayer bar coaters, and kiss coaters.

The drying conditions of the protective film forming composition are not particularly limited. However, when the composition for forming a protective film contains a solvent described below, it is preferable to perform heating and drying. Furthermore, the protective film forming composition containing a solvent is preferably heated and dried under conditions of 70°C to 130°C for 10 seconds to 5 minutes, for example. However, since the protective film-forming composition is thermosetting, it is preferable to heat and dry the composition itself and the thermosetting protective film-forming film formed from the composition without thermal curing.

Preferable protective film-forming films include, for example, a protective film-forming film containing a hardening accelerator (C). More preferable protective film-forming films include a polymer component (A), a thermosetting component (B). ), and the protective film forming film of the hardening accelerator (C). The polymer component (A) is considered to be a component formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component that performs a curing (polymerization) reaction using heat as a trigger factor for the reaction. In addition, in this specification, polymerization reaction includes polycondensation reaction. Hereinafter, the composition of the protective film forming composition will be described in detail.

<Protective film forming composition (III)> Preferred protective film-forming compositions include, for example, protective film-forming composition (III) containing a hardening accelerator (C) (herein, may be simply referred to as "composition (III)"). The protective film forming composition (III) preferably contains a polymer component (A), a thermosetting component (B), and a hardening accelerator (C).

[Polymer component (A)] The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to the protective film-forming film. in addition. In this specification, the polymer compound includes the product of polycondensation reaction.

The polymer component (A) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

Examples of the polymer component (A) include acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, and the like, and acrylic resin is preferred.

Examples of the acrylic resin in the polymer component (A) include known acrylic resins. The weight average molecular weight (Mw) of the acrylic resin is preferably 10000 to 2000000, more preferably 100000 to 1500000, further preferably 150000 to 1200000, particularly preferably 200000 to 1000000. When the weight average molecular weight of the acrylic resin is equal to or higher than the aforementioned lower limit, it is easier to increase the aforementioned E'(2) and E'(3). When the weight average molecular weight of the acrylic resin is less than the aforementioned upper limit, the protective film-forming film can more easily follow the uneven surface of the adherend.

In this specification, the "weight average molecular weight" refers to the polystyrene-converted value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) unless otherwise specified.

The glass transition temperature (Tg) of acrylic resin is preferably 0°C to 70°C, for example, it may be any of 0°C to 50°C, 0°C to 30°C, and 0°C to 10°C. A range, it can be any range of 10°C to 70°C, and 20°C to 70°C, or it can be any range of 10°C to 50°C, and 10°C to 30°C . When the Tg of the acrylic resin is equal to or higher than the lower limit, it is easier to adjust the E'(1), E'(2), and E'(3) to the target values. In addition, the adhesiveness between the cured material of the protective film-forming film and the support sheet can be suppressed, and the peelability of the support sheet can be appropriately improved. On the other hand, when the Tg of the acrylic resin is below the aforementioned upper limit, the adhesive force between the protective film-forming film and its cured product and the adherend can be improved.

There are m kinds of structural units in acrylic resin (m is an integer above 2). The m kinds of monomers from which these structural units are derived are numbered from 1 to m in sequence without repetition, and named "monomer m". In the case of ", the glass transition temperature (Tg) of acrylic resin can be calculated using Fox's mathematical formula as shown below.

[Mathematical formula 1] (In the mathematical formula, Tg is the glass transition temperature of acrylic resin; m is an integer above 2; Tg _k is the glass transition temperature of the homopolymer of monomer m; W _k is derived from monomer m in acrylic resin The mass fraction of the constituent unit m, but W _k satisfies the following mathematical formula.)

[Mathematical formula 2] (In the mathematical formula, m and W _k are the same as above.)

As the above-mentioned Tg _k , the value described in polymer materials, handbooks, adhesive handbooks, or Polymer handbooks can be used. For example, the Tg _k of the homopolymer of methyl acrylate is 10°C, the Tg _k of the homopolymer of methyl methacrylate is 105°C, and the Tg _k of the homopolymer of 2-hydroxyethyl acrylate is - At 15°C, the Tg _k of the homopolymer of glycidyl methacrylate is 41°C, the Tg _k of the homopolymer of 2-ethylhexyl acrylate is −70°C, and the Tg _k of the homopolymer of acrylic acid is is 103°C, the Tg _k of the homopolymer of acrylonitrile is 97°C, the Tg _k of the homopolymer of n-butyl acrylate is −54°C, and the Tg _k of the homopolymer of ethyl acrylate is −24° C.

Examples of the acrylic resin include: a polymer of one or more (meth)acrylate; selected from the aforementioned (meth)acrylate, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, Copolymers of two or more monomers such as styrene and N-hydroxymethylacrylamide, etc.

Examples of the (meth)acrylate constituting the acrylic resin include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid n-nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) ), tridecyl (meth)acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth)acrylic acid Cetyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute alkyl groups The alkyl group of the ester is a (meth)acrylic acid alkyl ester with a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid rings such as isobornyl acrylate and dicyclopentyl (meth)acrylate Alkyl esters; aralkyl (meth)acrylates such as benzyl (meth)acrylate; cycloalkenyl acrylates such as dicyclopentenyl (meth)acrylate; bicyclic (meth)acrylate (meth)acrylic acid cycloalkenyloxyalkyl esters such as pentenyloxyethyl ester; (meth)acrylic acid imide; (meth)acrylic acid glycidyl ester and other (meth)acrylic acid esters containing glycidyl groups; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid -2-Hydroxybutyl ester, (meth)acrylic acid-3-hydroxybutyl ester, (meth)acrylic acid-4-hydroxybutyl ester (meth)acrylate containing hydroxyl group; (meth)acrylic acid N-methylamine Ethyl esters and other (meth)acrylates containing substituted amine groups. Here, the "substituted amino group" means a group having a structure in which one or two hydrogen atoms of the amine group are replaced by groups other than hydrogen atoms.

In this specification, "(meth)acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid". Similar terms are used for (meth)acrylic acid. For example, "(meth)acrylyl" is a concept that includes both "acrylyl" and "methacrylyl", and "(meth)acrylate" ” is a concept that includes both “acrylate” and “methacrylate”.

The monomers constituting the acrylic resin may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

Acrylic resin may also have functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acrylyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanato groups. The aforementioned functional groups of the acrylic resin can also be bonded to other compounds through the cross-linking agent (F) described below, or can be directly bonded to other compounds without the cross-linking agent (F).

In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter, sometimes simply referred to as a “thermoplastic resin”) may be used alone instead of an acrylic resin, or may be used in combination with an acrylic resin. By using the aforementioned thermoplastic resin, the peelability of the protective film self-supporting sheet may be improved, or the protective film forming film may more easily follow the uneven surface of the adherend.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably 0°C to 70°C, for example, it may also be 0°C to 50°C, 0°C to 30°C, and 0°C to 10°C. Any range, it can be any range of 10°C to 70°C, and 20°C to 70°C, or it can be any one of 10°C to 50°C, and 10°C to 30°C Scope.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like.

The aforementioned thermoplastic resin contained in the composition (III) and the protective film-forming film may be only one type or two types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

In composition (III), regardless of the type of polymer component (A), the ratio of the content of polymer component (A) to the total content of all components except the solvent is preferably 10 mass% to 85 mass%, for example It can be any range of 10 mass% to 65 mass%, 10 mass% to 45 mass%, and 10 mass% to 30 mass%, or it can be 30 mass% to 85 mass%, and 50 mass% to 85 mass%. any range. This content is synonymous with the following: In the protective film-forming film, regardless of the type of polymer component (A), the ratio of the content of the polymer component (A) to the total mass of the protective film-forming film is preferably 10 mass % to 85 Mass %, for example, may be in any range of 10 mass % to 65 mass %, 10 mass % to 45 mass %, and 10 mass % to 30 mass %, or may be 30 mass % to 85 mass %, and 50 mass %. Any range from mass % to 85 mass %. This is based on the fact that the amount of components other than the solvent does not usually change during the process of forming a resin film by removing the solvent from the resin composition containing the solvent. The content of components other than the solvent between the resin composition and the resin film is The ratios are the same. Therefore, in this specification, the content of components other than the solvent is not limited to the case where the protective film is formed. Only the content in the resin film after removing the solvent from the resin composition is described.

The polymer component (A) may also be a thermosetting component (B). In the present invention, when the composition (III) contains such components that belong to both the polymer component (A) and the thermosetting component (B), it is deemed that the composition (III) contains the polymer. Component (A) and thermosetting component (B).

[Thermosetting ingredient (B)] The thermosetting component (B) is a component for hardening the protective film-forming film. The thermosetting component (B) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimide resins, unsaturated polyester resins, and the like, and epoxy thermosetting resins are preferred. In this specification, thermosetting polyimide resin is a general term for a polyimide precursor that forms a polyimide resin by thermal curing, and thermosetting polyimide.

(Epoxy thermosetting resin) The epoxy thermosetting resin is composed of, for example, an epoxy resin (B1) and a thermosetting agent (B2). In addition, the epoxy-based thermosetting resin may not contain the thermosetting agent (B2) but only the epoxy resin (B1). The epoxy-based thermosetting resin contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

･Epoxy resin (B1) Examples of the epoxy resin (B1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolak rings. Oxygen resin (o-cresol novolac epoxy resin), dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, benzene skeleton type epoxy Epoxy compounds with more than two functions such as resins.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but from the viewpoint of the hardening properties of the film formed from the protective film and the strength and heat resistance of the protective film, it is preferably 300 to 30,000, more preferably 300 to 10,000. The best value is 300 to 3000. The epoxy equivalent of the epoxy resin (B1) is preferably 100g/eq to 1000g/eq, more preferably 150g/eq to 950g/eq.

One type of epoxy resin (B1) may be used alone, or two or more types may be used in combination. When two or more types of epoxy resins (B1) are used in combination, the combination and ratio may be selected arbitrarily.

･Thermal hardener (B2) The thermal hardener (B2) functions as a hardener for the epoxy resin (B1). Examples of the thermal hardener (B2) include a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acidic group and the like, and preferably a phenolic hydroxyl group, an alcoholic hydroxyl group, an acidic group and an anhydride group. The group is preferably a phenolic hydroxyl group or an amine group.

Examples of the phenolic curing agent having a phenolic hydroxyl group among the thermal curing agents (B2) include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins. Phenol resin, etc. Among the thermal curing agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.

The thermal hardener (B2) may have an unsaturated hydrocarbon group.

When a phenolic hardener is used as the thermal hardener (B2), from the viewpoint of improving the peelability of the protective film self-supporting sheet, the thermal hardener (B2) is preferably a thermal hardener with a high softening point or glass transition temperature. .

In the thermal hardener (B2), the number average molecular weight of the resin components such as multifunctional phenol resin, novolac-type phenol resin, dicyclopentadiene-type phenol resin, aralkyl-type phenol resin, etc. is preferably 300 to 30,000, and more preferably 300 to 30,000. The best value is 400 to 10,000, especially the best value is 500 to 3,000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

One type of thermosetting agent (B2) may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio may be selected arbitrarily.

When a thermosetting agent (B2) is used, in the composition (III) and the protective film forming film, the content of the thermosetting agent (B2) relative to 100 parts by mass of the epoxy resin (B1) is preferably 0.1 Parts by mass to 100 parts by mass, preferably 0.5 parts by mass to 50 parts by mass, for example, any range from 0.5 parts by mass to 25 parts by mass, 0.5 parts by mass to 15 parts by mass, and 0.5 parts by mass to 7 parts by mass . When the content of the thermosetting agent (B2) is equal to or higher than the lower limit, the protective film-forming film can be cured more easily. By setting the content of the thermosetting agent (B2) below the upper limit, the moisture absorption rate of the protective film-forming film can be reduced, thereby improving the reliability of the package obtained using the protective film-forming film.

In the composition (III) and the protective film-forming film, the content of the thermosetting component (B) is 100 parts by mass relative to the total content of the polymer component (A) and the thermosetting component (B), preferably 10 parts by mass. to 70 parts by mass, more preferably 15 to 60 parts by mass, further preferably 20 to 50 parts by mass, for example, 25 to 40 parts by mass. When the aforementioned content of the thermosetting component (B) falls within these ranges, for example, the adhesion between the cured product of the protective film-forming film and the support sheet can be suppressed and the peelability of the support sheet can be improved. Here, when the thermosetting component (B) is an epoxy thermosetting resin, the "content of the thermosetting component (B)" is "the content of the thermosetting component (B)", and when a thermosetting agent (B2) is used, it is an epoxy resin. The total content of (B1) and thermosetting agent (B2) is the content of epoxy resin (B1) when thermosetting agent (B2) is not used.

[Harding accelerator (C)] The composition (III) and the protective film forming film may also contain a hardening accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III). Preferred hardening accelerators (C) include, for example, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 6-2 -(2-Methyl-1H-imidazol-1-yl)ethyl-1,3,5-triazine-2,4-diamine and other tertiary amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-undecylimidazole, etc. Imidazole (imidazole with one or more hydrogen atoms substituted by a group other than hydrogen atom); organic phosphine such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine with one or more hydrogen atoms substituted with organic group) ; Tetraphenylborate such as tetraphenylphosphonium tetraphenylboric acid, triphenylphosphine tetraphenylboric acid, etc.

The hardening accelerator (C) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

From the viewpoint of making it easier to adjust the storage elastic modulus E' (especially E'(1), E'(2), and E'(3)) of the first test piece and the second test piece, the hardening accelerator (C ) are preferably imidazoles.

When a hardening accelerator (C) is used, the content of the hardening accelerator (C) in the composition (III) and the protective film-forming film is preferably 100 parts by mass relative to the content of the thermosetting component (B). 1 to 13 parts by mass. For example, it may be any one of 3 to 13 parts by mass, 6 to 13 parts by mass, and 9 to 13 parts by mass. It may also be 1 to 10 parts by mass. Parts by mass, any range from 1 part by mass to 7 parts by mass, or 3 parts by mass to 10 parts by mass. By setting the aforementioned content of the hardening accelerator (C) to be equal to or more than the aforementioned lower limit, the effect of using the hardening accelerator (C) can be further significantly obtained. By keeping the content of the hardening accelerator (C) below the aforementioned upper limit, for example, the highly polar hardening accelerator (C) is inhibited from moving in the protective film-forming film to the protective film-forming film and the subject under high temperature/high humidity conditions. The segregation efficiency becomes higher due to the interface side between adherends. As a result, the reliability of the protective film-attached wafer obtained by using the protective film forming film is further improved.

[Filling material (D)] The composition (III) and the protective film-forming film preferably contain the filler (D). Since the protective film-forming film contains the filler (D), the storage elastic modulus E' (especially E'(1), E'(2)) of the first test piece and the second test piece can be more easily adjusted. , and E'(3)). More specifically, by adjusting the content of the filling material (D) of the protective film-forming film, the storage elastic modulus E' (especially E'(1)) of the first test piece and the second test piece can be more easily adjusted. , E'(2), and E'(3)). In addition, since the protective film-forming film contains the filler (D), it becomes easier to adjust the thermal expansion coefficient of the protective film-forming film and the protective film, and by optimizing the thermal expansion coefficient in accordance with the object to be formed of the protective film, it is further possible The reliability of a protective film-attached wafer obtained by using a protective film forming film is improved. In addition, since the protective film-forming film contains the filler (D), the moisture absorption rate of the protective film can be reduced or the heat dissipation property can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but an inorganic filler is preferred. Preferred inorganic fillers include, for example, silicon oxide, alumina, talc, calcium carbonate, titanium dioxide, titanium dioxide, silicon carbide, boron nitride and other powders; these inorganic fillers can be spherical Beads; surface modifications of these inorganic filler materials; single crystalline fibers of these inorganic filler materials; glass fibers, etc. Among them, the inorganic filler material is preferably silicon oxide or alumina, and more preferably silicon oxide.

From the viewpoint of improving the dispersibility of the filler (D) in the protective film-forming composition to other components, the silicon oxide is preferably a silicon oxide whose surface is modified with an organic group, and more preferably a silicon oxide with a vinyl or epoxy group. , phenyl, or methacryl group-modified silicon oxide on the surface, especially silicon oxide with a vinyl or epoxy group-modified surface.

From the viewpoint of improving the dispersibility of the filler (D) in the protective film-forming composition to the remaining components, the average particle size of the filler (D) is preferably 0.02 μm to 2 μm, more preferably 0.05 μm to 0.7 μm. Particularly preferred is 0.07 μm to 0.5 μm.

In this specification, "average particle diameter" means, unless otherwise specified, the particle diameter of a target object is observed using an electron microscope, 100 particles are randomly selected, and the arithmetic mean value ([ The total particle diameter of 100 particles when viewed from a plane]/100). Furthermore, as the particle diameter at this time, the maximum value of a line segment obtained by connecting any two points on the outer periphery of the particle when viewed from a plane can be used. For example, for particles in a resin film such as the filler (D) in a protective film-forming film, after the resin component disappears by calcining the resin film, the average particle size of the remaining particles is determined by the method described above. .

The filler material (D) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

When the filler material (D) is used, the ratio of the content of the filler material (D) in the protective film-forming film to the total mass of the protective film-forming film is preferably 20 mass % to 70 mass %. For example, it may also be It is any one of the ranges of 30 mass% to 70 mass%, 40 mass% to 70 mass%, and 50 mass% to 70 mass%. By falling into these ranges, the storage elastic modulus E' (especially E'(1), E'(2), and E'(3)).

[Coupling agent (E)] The composition (III) and the protective film-forming film may also contain the coupling agent (E). By using a coupling agent having a functional group that can react with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness of the protective film formed of the protective film-forming film to the adherend can be improved. In addition, by using the coupling agent (E), the protective film can improve the water resistance without impairing the heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (A), the thermosetting component (B), etc., and is preferably a silane coupling agent.

Preferable silane coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyltriethyloxysilane, imidazolesilane, etc.

The coupling agent (E) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

When a coupling agent (E) is used, the content of the coupling agent (E) in the composition (III) and the protective film-forming film is 100% relative to the total content of the polymer component (A) and the thermosetting component (B). Parts by mass are preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and particularly preferably 0.1 to 2 parts by mass. When the aforementioned content of the coupling agent (E) falls within these ranges, the chemical matching between the protective film-forming film and the adherend can be inhibited to a certain extent, making it easier to adjust the adhesion and peelability. On the other hand, since the aforementioned content of the coupling agent (E) is above the aforementioned lower limit, the effects caused by the use of the coupling agent (E) are more significantly exhibited, such as improving the dispersibility of the filler (D) in the resin, Improve the adhesion between the protective film forming film and the adherend, etc. By setting the aforementioned content of the coupling agent (E) to below the aforementioned upper limit, outgassing can be further suppressed.

[Crosslinking agent (F)] When using a component having functional groups such as a vinyl group, a (meth)acryl group, an amine group, a hydroxyl group, a carboxyl group, and an isocyanato group that can be bonded to other compounds such as the aforementioned acrylic resin as the polymer component (A), The composition (III) and the protective film-forming film may also contain a cross-linking agent (F). The cross-linking agent (F) is a component for cross-linking by bonding the aforementioned functional groups in the polymer component (A) to other compounds. By cross-linking in this way, the adhesive force of the protective film-forming film can be adjusted. and cohesion.

Examples of the cross-linking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate-based cross-linking agents (cross-linking agents having a metal chelate structure), and aziridine-based cross-linking agents. (Crosslinking agent with aziridine group) etc.

The cross-linking agent (F) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

From the viewpoint of improving the stability over time of the composition for forming a protective film, it is preferable that the composition (III) does not contain the cross-linking agent (F), or that the content of the cross-linking agent (F) in the composition (III) is small. , for example, the content of the cross-linking agent (F) relative to 100 parts by mass of the content of the polymer component (A) is less than 0.01 parts by mass. On the other hand, when more than a certain amount of the cross-linking agent (F) is used, the content of the cross-linking agent (F) in the composition (III) is 100 parts by mass relative to the content of the polymer component (A). Preferably it is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass. Since the aforementioned content of the cross-linking agent (F) is above the aforementioned lower limit, the effect of using the cross-linking agent (F) is more significantly demonstrated. When the content of the cross-linking agent (F) is equal to or less than the upper limit, excessive use of the cross-linking agent (F) can be suppressed.

[Energy ray curable resin (G)] The composition (III) and the protective film-forming film may contain energy ray curable resin (G). The protective film forming film contains energy ray curable resin (G) and can change its characteristics by irradiating energy rays.

The energy ray curable resin (G) is an energy ray curable compound, or can be regarded as an oligomer or polymer (polymer) synthesized from an energy ray curable compound. Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and preferably are acrylate compounds having a (meth)acrylyl group.

Examples of the acrylate compound include: trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, neopentylerythritol tri(meth)acrylate, Neopenterythritol tetra(meth)acrylate, dipenterythritol monohydroxypenta(meth)acrylate, dipenterythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate dicyclopentanyl di(meth)acrylate, 1,6-hexanediol di(meth)acrylate and other (meth)acrylates containing chain aliphatic skeleton; dicyclopentanyl di(meth)acrylate )acrylate) and other (meth)acrylates containing a cyclic aliphatic skeleton; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylic acid; oligoester (meth)acrylates; amines Formate (meth)acrylate oligomer; epoxy modified (meth)acrylate; polyether (meth)acrylate other than the aforementioned polyalkylene glycol (meth)acrylate; itaconic acid oligo Polymer etc.

The weight average molecular weight of the energy ray curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.

The energy ray curable compound used to synthesize the oligomer or polymer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily.

The energy ray curable resin (G) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily. .

In the case of using energy ray curable resin (G), in the composition (III), the ratio of the content of the energy ray curable resin (G) to the total mass of the composition (III) is preferably 1 mass % to 30 mass%, more preferably 5 to 25 mass%, particularly preferably 10 to 20 mass%.

[Photopolymerization initiator (H)] When the composition (III) and the protective film-forming film contain the energy ray curable resin (G), a photopolymerization initiator may be included in order to efficiently carry out the polymerization reaction of the energy ray curable resin (G). (H).

Examples of the photopolymerization initiator (H) in the composition (III) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoic acid, and benzoin methyl benzoate. , benzoin compounds such as benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenyl Ethane-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanyl)benzyl)phenyl)-2-methylpropan-1-one, 2 -(Dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone and other acetophenone compounds; bis(2,4,6-trimethylbenzyl) Phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other phosphine oxide compounds; benzylphenyl sulfide, tetramethylthiuram monosulfide and other thioether compounds; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; Acetyl and other diketone compounds; benzyl; diphenyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl- 1-[4-(1-methylvinyl)phenyl]acetone; 1-chloroanthraquinone, 2-chloroanthraquinone and other quinone compounds. Examples of the photopolymerization initiator (H) include photosensitizers such as amines.

The photopolymerization initiator (H) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily. .

When a photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III) is preferably 100 parts by mass relative to the content of the energy ray curable resin (G). It is 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.

[Color(I)] The composition (III) and the protective film-forming film preferably contain the colorant (I). By containing the colorant (I), the light transmittance of the protective film-forming film and the protective film can be easily adjusted.

Examples of the colorant (I) include known colorants such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include: amine-based pigments, cyanine-based pigments, merocyanine-based pigments, ketonium-based pigments, squalene-based pigments, azulium-based pigments, and polysulfide pigments. Methyl pigments, naphthoquinone pigments, pyranium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, pyrene Ketone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinphthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (Metal complex dyes), dithiol metal complex pigments, indolephenol pigments, triallylmethane pigments, anthraquinone pigments, naphthol pigments, methimine pigments, benzimidazole Ketone pigments, picanthrone pigments and Shilin pigments, etc.

Examples of the inorganic pigment include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, and ITO (Indium Tin Oxide, indium tin oxide) based pigments, ATO (Antimony Tin Oxide, antimony tin oxide) based pigments, etc.

The colorant (I) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these coloring agents (I) may be Take your pick.

When the colorant (I) is used, the content of the colorant (I) in the protective film-forming film can be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the protective film-forming film to adjust the light transmittance of the protective film-forming film, it is possible to adjust the printing legibility when laser printing is performed on the protective film-forming film or the protective film. . In addition, by adjusting the content of the colorant (I) in the protective film-forming film, the creativity of the protective film can be improved, or the grinding marks on the inner surface of the wafer can be made difficult to see. Taking these viewpoints into account, in the protective film-forming film, the content of the colorant (I) relative to the total mass of the protective film-forming film is preferably 0.1 mass % to 10 mass %, more preferably 0.1 mass % to 7.5 mass % %, preferably 0.1 mass% to 5 mass%. When the aforementioned ratio is equal to or higher than the aforementioned lower limit value, the effect of using the colorant (I) is more significantly exhibited. For example, when the protective film-forming film is peeled off from the adherend, it is easy to visually confirm whether the protective film-forming film remains on the adherend. When the ratio is equal to or less than the upper limit, excessive use of the colorant (I) can be suppressed.

[General purpose additive (J)] The composition (III) and the protective film-forming film may also contain a general-purpose additive (J) within the scope that does not impair the efficacy of the present invention. The general-purpose additive (J) may also be a well-known additive and can be selected arbitrarily according to the purpose. Although there is no particular limitation, preferred general-purpose additives include, for example: plasticizers, antistatic agents, antioxidants, getters, UV absorbers, etc.

The general-purpose additive (J) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be selected arbitrarily. The contents of the composition (III) and the general-purpose additive (J) for forming a protective film are not particularly limited and can be appropriately selected according to the purpose.

[solvent] The composition (III) preferably further contains a solvent. The composition (III) containing a solvent has good operability. In this specification, unless otherwise specified, "solvent" includes the concept of a dispersion medium used to disperse the target component in addition to dissolving the target component.

The aforementioned solvent is not particularly limited. Examples of preferred solvents include: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1-butanol Alcohols such as alcohol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amide such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds), etc. The solvent contained in composition (III) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these solvents may be selected arbitrarily.

Preferable examples of the solvent contained in the composition (III) include, for example, methyl ethyl ketone, toluene, and ethyl acetate from the viewpoint of allowing the components contained in the composition (III) to be mixed more uniformly. wait.

The content of the solvent in the composition (III) is not particularly limited. For example, it can be appropriately selected depending on the types of components other than the solvent.

<Production method of protective film forming composition (III)> Composition (III) can be obtained by blending each component constituting the composition. The order in which each component is added is not particularly limited, and two or more components may be added at the same time. The method of mixing the ingredients during preparation is not particularly limited, and any method can be appropriately selected from the following known methods: mixing by rotating a stirrer or stirring blade; mixing with a mixer; application of ultrasonic waves Mixing methods, etc. The temperature and time when adding and mixing each component are not particularly limited as long as the components are not deteriorated and can be adjusted appropriately. The temperature is preferably 15°C to 30°C.

◎Examples of protective film forming films FIG. 1 is a cross-sectional view schematically showing an example of the protective film-forming film according to this embodiment. In addition, the drawings used in the following description may show essential parts enlarged for convenience in order to facilitate understanding of the features of the present invention, and the dimensional ratios of each component may not be the same as the actual ones.

The protective film forming film 13 shown here is provided with a first release film 151 on one side (sometimes referred to as the "first side" in this specification) 13a, and on the other side opposite to the first side 13a. The second release film 152 is provided on the surface 13b (sometimes referred to as the "second surface" in this specification). This protective film forming film 13 is suitable for storage in a roll shape, for example.

When the aforementioned storage elastic modulus E' was measured on the first test piece produced using the protective film-forming film 13, the minimum value E'(1) was 45 MPa or less, and the maximum value E'(2) was 200 MPa. above. When the aforementioned storage elastic modulus E' was measured on the second test piece produced using the protective film-forming film 13, the minimum value E'(3) was 500 MPa or more.

The protective film forming film 13 can be formed using the above protective film forming composition.

Both the first release film 151 and the second release film 152 may be known ones. The first peeling film 151 and the second peeling film 152 may be the same as each other, or may be different from each other, for example, the peeling force required when peeling off the protective film forming film 13 is different from each other.

The protective film forming film 13 shown in FIG. 1 has an exposed surface formed by removing either the first release film 151 or the second release film 152 and is attached to the inner surface of the semiconductor wafer (not shown). noodle. In addition, when a support sheet or a dicing sheet described later is used, the exposed surface of the protective film forming film 13 produced by removing the remaining one of the first release film 151 and the second release film 152 becomes the same as the support sheet. Or the attached surface of the cutting piece.

Although FIG. 1 shows an example in which the release film is provided on both sides (the first side 13a and the second side 13b) of the protective film-forming film 13, the release film may be provided only on any one side of the protective film-forming film 13. That is, it is provided only on the first surface 13a or only on the second surface 13b.

As an example of a preferable protective film-forming film in this embodiment, a protective film-forming film is a thermosetting protective film-forming film; a laminate of a plurality of protective film-forming films having a width of 4 mm One test piece is held in two places with an interval of 20 mm, and the first test piece is heated from −20°C in the tensile mode at a constant temperature with a frequency of 11 Hz and a heating rate of 3°C/min. When the temperature is raised to 150°C and the storage elastic modulus E' of the first test piece is measured, the minimum value E' (1 ) is less than 45MPa, and the maximum value E'(2) of the aforementioned storage elastic modulus E' in the temperature range of 23°C to 70°C is more than 200MPa; the laminate of a plurality of pieces of the aforementioned protective film-forming film is thermally hardened The obtained hardened material and the second test piece with a width of 5 mm were held in two places with an interval of 20 mm, and were heated in a tensile mode at a constant speed with a frequency of 11 Hz and a heating rate of 3°C/min. When the second test piece is heated from −60°C to 350°C and the storage elastic modulus E' of the second test piece is measured, the storage elastic modulus E' is at a temperature of 23°C to 70°C. The minimum value E'(3) of the range is 500MPa or more; the protective film-forming film contains a polymer component (A), a thermosetting component (B) and a hardening accelerator (C); the polymer component (A) is acrylic acid Resin; the aforementioned thermosetting component (B) is composed of epoxy resin (B1) and thermosetting agent (B2), or does not include thermosetting agent (B2) and is composed of only epoxy resin (B1) (also That is, it is an epoxy thermosetting resin); the hardening accelerator (C) is an imidazole. This protective film-forming film may further contain one or both of a filling material (D) and a coloring agent (I). The aforementioned filling material (D) may also be a surface modification of silicon oxide or aluminum oxide (alumina). Taste.

As another preferred example of the protective film-forming film of this embodiment, a protective film-forming film is a thermosetting protective film-forming film; a laminate of a plurality of protective film-forming films having a width of 4 mm One test piece is held in two places with an interval of 20 mm, and the first test piece is heated from −20°C in the tensile mode at a constant temperature with a frequency of 11 Hz and a heating rate of 3°C/min. When the temperature is raised to 150°C and the storage elastic modulus E' of the first test piece is measured, the minimum value E' (1 ) is less than 45MPa, and the maximum value E'(2) of the aforementioned storage elastic modulus E' in the temperature range of 23°C to 70°C is more than 200MPa; the laminate of a plurality of pieces of the aforementioned protective film-forming film is thermally hardened The obtained hardened material and the second test piece with a width of 5 mm were held in two places with an interval of 20 mm, and were heated in a tensile mode at a constant speed with a frequency of 11 Hz and a heating rate of 3°C/min. When the second test piece is heated from −60°C to 350°C and the storage elastic modulus E' of the second test piece is measured, the storage elastic modulus E' is at a temperature of 23°C to 70°C. The minimum value E'(3) of the range is 500MPa or more; the protective film-forming film contains a polymer component (A), a thermosetting component (B) and a hardening accelerator (C); the polymer component (A) is acrylic acid Resin; the aforementioned thermosetting component (B) is composed of epoxy resin (B1) and thermosetting agent (B2), or does not include thermosetting agent (B2) and is composed of only epoxy resin (B1) (also That is, it is an epoxy thermosetting resin); the hardening accelerator (C) is an imidazole; in the protective film-forming film, the content of the polymer component (A) is relative to the total mass of the protective film-forming film. The ratio is 10% by mass to 85% by mass; in the aforementioned protective film-forming film, the content of the aforementioned thermosetting component (B) is 100 parts by mass relative to the total content of the aforementioned polymer component (A) and the thermosetting component (B). 10 to 70 parts by mass; in the protective film forming film, the content of the hardening accelerator (C) is 1 to 13 parts by mass relative to 100 parts by mass of the thermosetting component (B); When the protective film-forming film contains the thermosetting agent (B2), the content of the thermosetting agent (B2) in the protective film-forming film is 0.1 parts by mass relative to 100 parts by mass of the epoxy resin (B1). parts to 100 parts by mass; in the aforementioned protective film-forming film, the ratio of the total content of the aforementioned polymer component (A), thermosetting component (B) and hardening accelerator (C) to the total mass of the aforementioned protective film-forming film Not more than 100% by mass. In the protective film-forming film of this other example, the aforementioned polymer component (A), thermosetting component (B), epoxy resin (B1), thermosetting agent (B2), and hardening accelerator (C) are contained in the aforementioned contents. Furthermore, it may be within any of the numerical ranges explained above.

This other example of the protective film forming film may further contain one or both of the filling material (D) and the coloring agent (I). In this case, the aforementioned filling material (D) is silicon oxide or aluminum oxide. ); when the protective film-forming film contains the filling material (D), the content of the filling material (D) in the protective film-forming film is the ratio of the total mass of the protective film-forming film to the total mass of the protective film-forming film. The ratio is 20 mass% to 70 mass%; when the protective film-forming film contains the colorant (I), the content of the colorant (I) in the protective film-forming film is relative to the content of the protective film-forming film. The ratio of the total mass is 0.1 mass% to 10 mass%; in the aforementioned protective film forming film, the aforementioned polymer component (A), thermosetting component (B), hardening accelerator (C), filler material (D) and The ratio of the total content of the colorants (I) to the total mass of the protective film-forming film does not exceed 100% by mass. In this other example of the protective film-forming film, the aforementioned filler material (D) may also be silicon oxide whose surface is modified with a vinyl group, an epoxy group, a phenyl group or a methacrylic group. In this other example of the protective film-forming film, the aforementioned polymer component (A), thermosetting component (B), epoxy resin (B1), thermosetting agent (B2), hardening accelerator (C), filler The aforementioned contents of the material (D) and the colorant (I) may further fall within any of the numerical ranges explained above.

By using the protective film-forming film of this embodiment together with a support sheet described later, the protective film can be formed and cut simultaneously, and a composite sheet for protective film formation can be constructed. The composite sheet for forming a protective film will be described below.

◇Composite sheet for protective film formation A composite sheet for forming a protective film according to an embodiment of the present invention is provided with: a support sheet, and a protective film-forming film provided on one side of the support sheet; the protective film-forming film is the protective film according to the above-mentioned embodiment of the present invention. Form a film. The protective film-forming composite sheet of this embodiment can be attached to a target portion of the workpiece (for example, the inner surface of the wafer) with the protective film-forming film.

In this specification, even after the protective film-forming film is cured, as long as the laminated structure of the supporting sheet and the cured product of the protective film-forming film is maintained, the laminated structure is called a "composite sheet for protective film formation."

Each layer constituting the composite sheet for forming a protective film will be described in detail below.

◎Support piece The aforementioned supporting sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other. The combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

The support sheet can be transparent or opaque, and can also be colored according to the purpose. When the protective film-forming film has energy ray curability, it is preferable that the support sheet allows energy rays to pass through it.

Examples of the support sheet include a support sheet including a base material and an adhesive layer provided on one side of the base material; a support sheet consisting only of the base material; and the like. When the support sheet has an adhesive layer, the adhesive layer is disposed between the base material and the protective film-forming film in the protective film-forming composite sheet.

When a support sheet including a base material and an adhesive layer is used, the adhesiveness and peelability between the support sheet and the protective film-forming film in the composite sheet for protective film formation can be easily adjusted. When a support sheet composed only of a base material is used, a composite sheet for forming a protective film can be produced at low cost.

Hereinafter, examples of the composite sheet for forming a protective film according to the present embodiment will be described for each type of such support sheet with reference to the drawings.

◎An example of composite sheet for protective film formation FIG. 2 is a cross-sectional view schematically showing an example of the composite sheet for forming a protective film according to this embodiment. In addition, in the drawings following FIG. 2 , the same components shown in the previously described drawings are assigned the same reference numerals as in the previously described drawings, and detailed descriptions of the components are omitted.

The protective film-forming composite sheet 101 shown here is constituted by a support sheet 10 and a protective film-forming sheet provided on one side (sometimes referred to as the “first side” in this specification) 10 a of the support sheet 10 Membrane 13. The support sheet 10 is composed of a base material 11 and an adhesive layer 12 provided on one side (first side) 11 a of the base material 11 . In the protective film-forming composite sheet 101 , the adhesive layer 12 is disposed between the base material 11 and the protective film-forming film 13 . That is, the protective film-forming composite sheet 101 is composed of the base material 11, the adhesive layer 12, and the protective film-forming film 13, which are sequentially laminated in the thickness direction of these layers. The first surface 10a of the support sheet 10 is the same as the surface 12a of the adhesive layer 12 on the opposite side to the base material 11 side (sometimes referred to as the "first surface" in this specification).

The protective film forming composite sheet 101 further includes a jig adhesive layer 16 and a release film 15 on the protective film forming film 13 . In the protective film-forming composite sheet 101, the protective film-forming film 13 is laminated on the entire surface or almost the entire surface of the first surface 12a of the adhesive layer 12, and on the adhesive layer 12 side of the protective film-forming film 13 The jig adhesive layer 16 is laminated on a part of the opposite surface (sometimes referred to as the "first surface" in this specification) 13a, that is, in the area near the peripheral edge. Furthermore, among the first surface 13a of the protective film-forming film 13, there are areas where the jig adhesive layer 16 is not laminated, and the surface of the jig adhesive layer 16 opposite to the protective film-forming film 13 side ( In this specification, (sometimes called "first surface") 16a, the release film 15 is laminated|stacked. The support sheet 10 is provided on the surface 13b of the protective film forming film 13 opposite to the first surface 13a (sometimes referred to as the “second surface” in this specification).

It is not limited to the case of the protective film-forming composite sheet 101. In the protective film-forming composite sheet of this embodiment, the release film (for example, the release film 15 shown in FIG. 2) has an arbitrary structure. The protective film of this embodiment is formed The composite sheet may or may not have a release film.

The jig adhesive layer 16 is used to fix the protective film forming composite sheet 101 to a jig such as a ring frame. The adhesive layer 16 for a jig may have, for example, a single-layer structure containing an adhesive component or an adhesive component, or may have a multi-layer structure including a sheet as a core material, and adhesive-containing adhesive layers provided on both sides of the sheet. layer of agent ingredients or adhesive ingredients.

In the state where the protective film forming composite sheet 101 has the release film 15 removed, the inner surface of the semiconductor wafer is attached to the first surface 13 a of the protective film forming film 13 , and further, the first surface of the jig adhesive layer 16 The surface 16a is attached to a jig such as a ring frame and used.

FIG. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to this embodiment. The composite sheet 102 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in FIG. 2 except that the size of the protective film forming film is different and it does not include the adhesive layer 16 for a jig. .

More specifically, in the protective film-forming composite sheet 102, the protective film-forming film 23 is laminated on a part of the first surface 12a of the adhesive layer 12 (that is, in the width direction of the adhesive layer 12 (in FIG. 3 The area on the central side of the left and right directions). In addition, the release film 15 is laminated on the surface 23a of the protective film forming film 23 on the side opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in this specification) and the first surface of the adhesive layer 12 12a is an area where the protective film forming film 23 is not laminated. The support sheet 10 is provided on the surface 23b of the protective film forming film 23 located on the opposite side to the first surface 23a (sometimes referred to as the "second surface" in this specification).

The composite sheet for forming a protective film according to this embodiment is not limited to that shown in FIGS. 2 to 3 , and the ones shown in FIGS. 2 to 3 may be modified or part of the structure may be deleted within the scope that does not impair the effect of the present invention. , it is also possible to add other structures to those described so far.

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

○Substrate The base material is in the form of a sheet or film, and examples of the constituent material of the base material include various resins. Examples of the aforementioned resin include polyethylene such as low density polyethylene (LDPE; low density polyethylene), linear low density polyethylene (LLDPE; linear low density polyethylene), and high density polyethylene (HDPE; high density polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- Ethylene-based copolymers such as (meth)acrylate copolymers and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resins obtained from ethylene as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Polyesters such as diesters, polyethylene-2,6-naphthalate, fully aromatic polyesters in which all structural units have aromatic cyclic groups; copolymers of two or more polyesters; poly(meth)acrylic acid Ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; poly Silica; polyetherketone, etc. Examples of the resin include polymer alloys such as mixtures of the polyester and resins other than the polyester. The polymer alloy of the polyester and the resin other than the polyester preferably contains a relatively small amount of the resin other than the polyester. Examples of the resin include: a cross-linked resin obtained by cross-linking one or more of the above-described resins; and a modified ionic polymer using one or two or more of the above-described resins. resin. From the viewpoint of excellent heat resistance, the resin is preferably polypropylene or polybutylene terephthalate.

The resin constituting the base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these resins may be selected arbitrarily.

The base material may also be composed of one layer (single layer), or may be composed of two or more layers. When the base material is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the base material is preferably 50 μm to 300 μm, more preferably 60 μm to 100 μm. When the thickness of the base material is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion suitability to the wafer can be 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 multiple layers means the total thickness of all the layers constituting the base material.

In addition to the main constituent materials such as the aforementioned resin, the base material may also contain various well-known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

The base material can be transparent or opaque, and can be colored according to the purpose, or other layers can be evaporated. When the protective film-forming film has energy ray curability, it is preferable that the base material allows energy rays to penetrate.

In order to adjust the adhesion of the base material to the layer provided on the base material (such as an adhesive layer, a protective film-forming film, or other layers mentioned above), the following treatments can also be applied to the surface: sandblasting, solvent treatment, etc. Chemical treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; lipophilic treatment; hydrophilic treatment, etc. In addition, the surface of the substrate can also be primed.

The base material can also be adhesive on at least one side by containing a specific range of components (such as resin, etc.).

The base material can be produced by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the aforementioned resin.

○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film and contains adhesive. Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin.

The adhesive layer may also be composed of one layer (single layer), or may be composed of two or more layers. When the adhesive layer is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 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 an adhesive layer composed of multiple layers means the total thickness of all the layers constituting the adhesive layer.

The adhesive layer may be transparent or opaque, and may be colored according to the purpose. When the protective film-forming film has energy ray curability, the adhesive layer preferably allows energy rays to pass through it.

The adhesive layer may be energy ray curable or non-energy ray curable. The energy ray curable adhesive layer can adjust its physical properties before and after hardening. For example, by hardening the energy ray curable adhesive layer before picking up the semiconductor wafer with the protective film forming film described later, the semiconductor wafer with the protective film forming film can be picked up more easily.

In this specification, even after the energy ray curable adhesive layer is cured by energy rays, as long as the laminated structure of the hardened product of the base material and the energy ray curable adhesive layer is maintained, this laminated structure is also called a "support sheet" .

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, by applying an adhesive composition to the surface to be formed of the adhesive layer and drying as necessary, the adhesive layer can be formed on the target site. The content ratio of the components that do not vaporize at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components before the adhesive layer.

The application and drying of the adhesive composition can be performed, for example, by the same method as the above-described application and drying of the protective film forming composition.

When the adhesive layer is energy ray curable, examples of the energy ray curable adhesive composition include: a non-energy ray curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive"). adhesive resin (I-1a)"), an adhesive composition (I-1) of an energy ray curable compound; an adhesive composition (I-1) containing an unsaturated group introduced into the side chain of a non-energy ray curable adhesive resin (I-1a) Adhesive composition (I-2) of energy ray curable adhesive resin (I-2a) (hereinafter sometimes referred to as "adhesive resin (I-2a)"); containing the aforementioned adhesive resin (I-2a) ), energy ray curable compound adhesive composition (I-3), etc.

When the adhesive layer is non-energy ray curable, examples of the non-energy ray curable adhesive composition include an adhesive composition (I-1a) containing the aforementioned non-energy ray curable adhesive resin. I-4) etc.

[Non-energy ray curable adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably an acrylic resin. Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

The acrylic polymer preferably has 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 that becomes a starting point for crosslinking by reacting the functional group with a crosslinking agent described later. Examples of the functional group-containing monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, epoxy group-containing monomers, and the like.

The acrylic polymer may further have structural units derived from other monomers, in addition to structural units derived from alkyl (meth)acrylate and functional group-containing monomers. The other monomers mentioned above are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate and the like. Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

The aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3) and adhesive composition (I-4) (hereinafter including these adhesive compositions, referred to as Among the "adhesive compositions (I-1) to adhesive compositions (I-4)"), the aforementioned acrylic polymer and other aforementioned acrylic resins may have only one type of structural unit or two or more types. , in the case of two or more situations, the combination and ratio of these structural units can be selected arbitrarily.

The adhesive resin (I-1a) contained in the adhesive composition (I-1) or the adhesive composition (I-4) may be only one type, or may be two or more types, and in the case of two or more types , the combination and ratio of these adhesive resins (I-1a) can be selected arbitrarily.

In the adhesive layer formed from the adhesive composition (I-1) or the adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive layer Preferably it is 5 mass % to 99 mass %.

[Energy ray curable adhesive resin (I-2a)] The adhesive resin (I-2a) can be obtained, for example, by reacting an unsaturated group-containing compound having an energy-beam polymerizable unsaturated group with a functional group in the adhesive resin (I-1a).

In addition to the energy-beam polymerizable unsaturated group, the compound containing an unsaturated group further has the ability to bond with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). A compound that is the basis of knots. Examples of the energy ray polymerizable unsaturated group include: (meth)acrylyl group, vinyl (ethenyl), allyl (2-propenyl), etc., with (meth)acrylyl group being preferred. . Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amine group, and a carboxyl group or an epoxy group. base-bonded hydroxyl and amine groups, etc.

Examples of the compound containing an unsaturated group include (meth)acryloxyethyl isocyanate, (meth)acryloxyethyl isocyanate, glycidyl (meth)acrylate, and the like.

The adhesive resin (I-2a) contained in the adhesive composition (I-2) or the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, , you can choose any of these combinations and ratios.

In the adhesive layer formed by the adhesive composition (I-2) or the adhesive composition (I-3), the content of the adhesive resin (I-2a) relative to the total mass of the aforementioned adhesive layer The ratio is preferably 5% by mass to 99% by mass.

[Energy ray curing compound] Examples of the energy-beam-curable compound contained in the adhesive composition (I-1) or the adhesive composition (I-3) include energy-beam-polymerizable unsaturated groups that can be cured by irradiation with energy-beams. And hardened monomers or oligomers.

Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylic acid amine Formate; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of oligomers include oligomers of polymers of the monomers exemplified above.

The aforementioned energy ray curable compound contained in the adhesive composition (I-1) or the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, The combination and ratio of these energy ray curable compounds can be selected arbitrarily.

In the adhesive layer formed from the adhesive composition (I-1) or the adhesive composition (I-3), the ratio of the content of the energy ray curable compound to the total mass of the adhesive layer, Preferably it is 1 mass % to 95 mass %.

[Cross-linking agent] As the adhesive resin (I-1a), when the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate is used, The adhesive composition (I-1) or the adhesive composition (I-4) preferably further contains a cross-linking agent. In addition, as the adhesive resin (I-2a), for example, when the aforementioned acrylic polymer having the same structural unit derived from the functional group-containing monomer as the adhesive resin (I-1a) is used, the adhesive composition The compound (I-2) or the adhesive composition (I-3) may further contain a cross-linking agent.

For example, the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a) or the adhesive resins (I-2a). Examples of the cross-linking agent include isocyanate-based cross-linking agents (cross-linking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy cross-linking agents (cross-linking agents with glycidyl groups) such as ethylene glycol glycidyl ether; aziridine cross-linking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphine triazine Cross-linking agent (cross-linking agent with aziridine group); metal chelate such as aluminum chelate is cross-linking agent (cross-linking agent with metal chelate structure); isocyanurate is cross-linking agent ( Cross-linking agent with isocyanuric acid skeleton), etc.

The cross-linking agent contained in the adhesive composition (I-1) to the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, these cross-linking agents The combination and ratio can be selected arbitrarily.

In the aforementioned adhesive composition (I-1) or adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). parts to 50 parts by mass. In the aforementioned adhesive composition (I-2) or adhesive composition (I-3), the content of the cross-linking agent is preferably 0.01 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). parts to 50 parts by mass.

[Photopolymerization initiator] Adhesive composition (I-1), adhesive composition (I-2) and adhesive composition (I-3) (hereinafter including these adhesive compositions, referred to as "adhesive composition (I-1)" The adhesive composition (I-3)") may further contain a photopolymerization initiator. The adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator can fully proceed with the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include the same ones as the photopolymerization initiator (H) described above.

The photopolymerization initiator contained in the adhesive compositions (I-1) to (I-3) may be only one type, or may be two or more types. In the case of two or more types, these photopolymerization initiators may The combination and ratio of polymerization initiators can be selected arbitrarily.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the energy ray curable compound. In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass.

[Other additives] The adhesive compositions (I-1) to (I-4) may also contain other additives that are not equivalent to any of the above components within the scope that does not impair the efficacy of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. , reaction retardants, cross-linking accelerators (catalysts) and other well-known additives. In addition, the so-called reaction retardant is used to inhibit the action of the catalyst mixed in the adhesive composition (I-1) to the adhesive composition (I-4), for example, causing the adhesive composition to be stored during storage. (I-1) A component that undergoes an unexpected cross-linking reaction in the adhesive composition (I-4). Examples of the reaction retardant include those that form a chelate complex with a chelate compound for a catalyst. More specifically, those having two or more carbonyl groups (-C(=O)-) in one molecule By.

The other additives contained in the adhesive compositions (I-1) to (I-4) may be only one type, or may be two or more types. In the case of two or more types, these other additives The combination and ratio can be selected arbitrarily.

The content of other additives in the adhesive composition (I-1) to the adhesive composition (I-4) is not particularly limited, and may be appropriately selected according to the type of additive.

[solvent] The adhesive compositions (I-1) to (I-4) may also contain a solvent. Since the adhesive compositions (I-1) to (I-4) contain a solvent, the coating suitability for the surface to be coated can be improved.

The aforementioned solvent is preferably an organic solvent. Examples of the aforementioned organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, etc.

The solvent contained in the adhesive composition (I-1) to the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these solvents You can choose whatever you want.

The content of the solvent in the adhesive composition (I-1) to the adhesive composition (I-4) is not particularly limited as long as it can be appropriately adjusted.

○Manufacturing method of adhesive composition The adhesive composition can be produced in the same manner as in the case of the protective film forming composition described above, except for differences in the types of ingredients.

◇Manufacturing method of composite sheet for protective film formation The composite sheet for forming a protective film can be produced by laminating the above-mentioned layers in a corresponding positional relationship and adjusting the shape of some or all of the layers as necessary. The formation methods of each layer are as described above.

For example, when manufacturing a support sheet and laminating an adhesive layer on a base material, it is sufficient to apply the above-mentioned adhesive composition on the base material and dry it if necessary. In addition, even the method of forming an adhesive layer on the release film in advance by applying an adhesive composition on the release film and drying it if necessary, and attaching the exposed surface of the adhesive layer to a surface of the base material is also applicable. An adhesive layer can be laminated on the substrate. At this time, the adhesive composition is preferably applied to the release-treated surface of the release film. In addition, the release film in this case may be removed during the manufacturing process of the protective film-forming composite sheet or at any point in time during use. So far, the example of laminating an adhesive layer on a base material has been exemplified. However, the above method can also be applied to a case where, for example, other layers other than the adhesive layer are laminated on a base material.

On the other hand, for example, when a protective film is laminated on an adhesive layer laminated on a substrate to form a film, the protective film-forming composition can be applied on the adhesive layer to directly form a protective film-forming film. The composition for forming this layer can also be used as a layer other than the protective film-forming film, and this layer can be laminated on the adhesive layer in the same manner. In this way, a new layer (hereinafter referred to as the "second layer") is formed on any layer laminated on the substrate (hereinafter referred to as the "first layer") to form a continuous two-layer laminated structure (in other words In the case of a laminated structure of a first layer and a second layer), the following method can be applied: apply a composition for forming the second layer on the first layer, and dry it if necessary. Among them, the second layer is preferably formed in advance on the release film by using a composition for forming the second layer, and the exposed portion of the formed second layer on the opposite side to the side that is in contact with the release film The surface is attached to the exposed surface of the first layer to form a continuous two-layer laminated structure. At this time, the composition is preferably applied to the release-treated surface of the release film. The peel-off film can be removed if necessary after forming a laminated structure. Here, the case where a protective film is laminated on an adhesive layer to form a film is given as an example. However, for example, when a layer (film) other than a protective film is laminated on an adhesive layer, the target laminate structure can be selected arbitrarily. .

In this way, since the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of forming it in advance on the release film and then attaching it to the surface of the target layer, it is only necessary to select the layer that adopts this step as needed. , to produce a composite sheet for protective film formation.

In addition, the composite sheet for protective film formation is usually stored with a release film attached to the surface of the outermost layer (for example, the protective film forming film) on the opposite side to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a protective film-forming composition, is coated on the release film (preferably the release-treated surface of the release film), and dried if necessary to preform a layer on the release film. The layer that constitutes the outermost layer is stacked on the exposed surface of the layer opposite to the side that is in contact with the release film, and the remaining layers are kept attached without removing the release film, thereby obtaining the protection of the release film. Composite sheet for film formation.

◇Methods for manufacturing semiconductor devices (how to use protective film-forming films and protective film-forming composite sheets) The protective film-forming film and the protective film-forming composite sheet can be used to manufacture the semiconductor wafer with the protective film, and further, the semiconductor wafer with the protective film can be used to manufacture a semiconductor device.

The manufacturing method of a semiconductor device according to this embodiment includes an attaching step of attaching one side of the protective film-forming film or the exposed surface of the protective film-forming film in the protective film-forming composite sheet to a semiconductor wafer. The inner surface of Performing laser printing, when using the protective film-forming film that does not constitute the protective film-forming composite sheet, performs laser printing on the other side of the protective film-forming film; the processing step is after the aforementioned printing step, When using the composite sheet for forming a protective film, the semiconductor wafer is divided into semiconductor wafers on the supporting sheet in the composite sheet for forming a protective film, and the protective film is cut along the divided parts of the semiconductor wafer. When the film-forming film is used without forming the protective film-forming composite sheet, a dicing sheet is attached to the other side of the protective film-forming film, and then the semiconductor is placed on the dicing sheet. The wafer is divided into semiconductor wafers, and the protective film-forming film is cut along the division points of the semiconductor wafer to produce a semiconductor wafer with a protective film-forming film, which includes the semiconductor wafer and a semiconductor chip provided on the semiconductor wafer. The aforementioned protective film-forming film on the inner surface is cut off; the picking-up step is after the aforementioned processing step, the semiconductor wafer with the protective film-forming film is pulled away from the aforementioned cutting piece or the supporting piece; and the bonding step is After the aforementioned pickup step, the protruding electrodes in the picked up semiconductor wafer with the aforementioned protective film-forming film are flip-chip connected to the circuit surface of the substrate, so that the aforementioned semiconductor wafer with the aforementioned protective film-forming film is bonded. In the thermal hardening step on the circuit surface, after the bonding step, the protective film forming film in the semiconductor wafer with the protective film forming film is thermally cured to form a protective film.

Hereinafter, a method of manufacturing a semiconductor device will be described with reference to drawings. 4A to 4F are schematically illustrating an example of the manufacturing method when a protective film forming composite sheet is used in the manufacturing method of the semiconductor device according to the present embodiment (in this specification, it is sometimes referred to as "the manufacturing method"). (1)") cross-sectional view. Here, a case of using the protective film forming composite sheet 101 shown in FIG. 2 will be described.

＜＜Manufacturing method (1)＞＞ ＜Attachment steps＞ In the aforementioned attaching step of the aforementioned manufacturing method (1), as shown in FIG. 4A , the protective film forming film 13 in the protective film forming composite sheet 101 with the release film 15 removed is attached to the semiconductor wafer. The inner surface 9b of 9 is used to manufacture a semiconductor wafer 901 with a protective film forming film. The protective film forming film 13 is attached to the inner surface 9 b of the semiconductor wafer 9 with the first surface 13 a as its exposed surface. In FIG. 4A , symbol 9 a indicates the circuit surface of the semiconductor wafer 9 .

Among them, in FIGS. 4A to 4F , illustrations of circuits and protruding electrodes in the semiconductor wafer or the circuit surface of the semiconductor wafer are omitted. This is also the same in the following pictures.

The protective film forming film 13 can be attached to the semiconductor wafer 9 by a known method such as using a roller.

The conditions for attaching the protective film forming film 13 to the semiconductor wafer 9 are not particularly limited. Generally, the temperature of the protective film forming film 13 during attachment (attachment temperature) is preferably 20°C to 100°C, more preferably 65°C to 75°C. The speed at which the protective film-forming film 13 is attached (attaching speed) is preferably 0.1 m/min to 2 m/min, and the pressure (attachment pressure) applied to the protective film-forming film 13 during attachment is preferably 0.1 MPa to 0.6 MPa.

The E'(1) of the first test piece produced by using the self-protective film-forming film 13 is 45 MPa or less. In the attachment step, the protective film-forming film 13 has good adhesion to the semiconductor wafer 9. For example, in the semiconductor wafer 901 with the protective film forming film, peeling of the protective film forming film 13 from the semiconductor wafer 9 can be suppressed even in a cooled state.

＜Print steps＞ Manufacturing method (1) After the above-mentioned attaching step, in the above-mentioned printing step, as shown in FIG. 4B , by attaching the surface of the protective film-forming composite sheet 101 located on the support sheet 10 side of the protective film-forming film 13 (also That is, the second surface 13b) is irradiated with laser light R to perform laser printing on the surface. Laser printing can be performed by known methods. For example, by setting the wavelength of the laser light R to 532nm, setting the frequency of the laser light to 20 kHz to 40 kHz, and setting the scanning speed to 100 mm/s to 300 mm/s to irradiate the laser light R, it is possible to achieve a good method for laser printing. The wavelength of the laser light R can also be selected from other wavelengths.

The E'(2) of the first test piece produced by the self-protective film-forming film 13 is 200 MPa or more, and the protective film-forming film 13 after the printing step (more specifically, the second side of the protective film-forming film 13 13b), capable of forming printed characters in a clear manner.

＜Processing steps＞ Manufacturing method (1) After the above-mentioned printing step, in the above-mentioned processing step, the semiconductor wafer 9 is divided into semiconductor wafers 90 on the support sheet 10 in the protective film forming composite sheet 101, and The protective film is cut at the dividing point to form film 13. Thereby, as shown in FIG. 4C , a semiconductor wafer 913 with a protective film forming film is manufactured, which includes a semiconductor wafer 90 and the cut protective film forming film 130 provided on the inner surface 90 b of the semiconductor wafer 90 , and is manufactured. The semiconductor wafer group 902 with a protective film forming film is composed of a plurality of semiconductor wafers 913 with a protective film forming film arranged in order and fixed on the support sheet 10 . In FIG. 4C , symbol 130 a indicates the first surface of the protective film forming film 130 after cutting, and corresponds to the first surface 13 a of the protective film forming film 13 . In addition, reference numeral 130 b indicates the second surface of the protective film-forming film 130 after cutting, and corresponds to the second surface 13 b of the protective film-forming film 13 . In addition, reference numeral 90 a indicates a circuit surface of the semiconductor wafer 90 and corresponds to the circuit surface 9 a of the semiconductor wafer 9 .

In the processing step of the manufacturing method (1), for example, the semiconductor wafer 9 may be divided and the protective film forming film 13 may be cut at the same time, or the semiconductor wafer 9 may be divided first and then the protective film forming film 13 may be cut. In the manufacturing method (1), regardless of the order, when the dividing of the semiconductor wafer and the cutting of the protective film forming film are continuously performed by the same operation in an uninterrupted manner, the semiconductor wafer is deemed to be performed simultaneously. The separation and protective film forming film are cut off.

The division of the semiconductor wafer 9 and the cutting of the protective film forming film 13 can be performed by known methods according to the order of performing these.

For example, the semiconductor wafer 9 can be divided and the protective film can be formed simultaneously by various cutting methods such as knife cutting using a blade, laser cutting using laser light irradiation, or water cutting using water containing abrasives. Cutting of membrane 13. In addition, the modified layer is formed by stealth dicing (registered trademark), and the undivided semiconductor wafer 9 and the protective film forming film 13 are simultaneously stretched in a direction parallel to the surfaces, that is, a so-called expansion method is performed. , the semiconductor wafer 9 can also be divided and the protective film forming film 13 can be cut simultaneously. This expansion method is preferably carried out at low temperatures such as −20°C to 5°C.

Invisible cutting (registered trademark) is the method described below. That is, first, a predetermined division point is preset inside the semiconductor wafer, and this point is used as a focus. By focusing the laser light on this focus, a modified layer is formed inside the semiconductor wafer. The modified layer of the semiconductor wafer is different from other parts of the semiconductor wafer. It is modified by laser light irradiation, so the intensity becomes weaker. Therefore, by applying an external force to the semiconductor wafer, cracks are generated in the modified layer inside the semiconductor wafer toward both sides of the semiconductor wafer, and become the starting point for dividing the semiconductor wafer. Then, an external force is applied to the semiconductor wafer, and the semiconductor wafer is divided at the portion of the modified layer, thereby manufacturing a semiconductor wafer.

＜Pickup steps＞ Manufacturing method (1) After the aforementioned processing steps, in the aforementioned picking up step, as shown in FIG. 4D , the semiconductor wafer 913 with the protective film forming film is pulled away from the supporting sheet 10 and picked up. In the pick-up step of the manufacturing method (1), the second surface 130b of the protective film-forming film 130 in the semiconductor wafer 913 with the protective film-forming film and the first surface 12a of the adhesive layer 12 in the support sheet 10 occur. Strip.

The semiconductor wafer 913 with the protective film forming film can also be picked up by a known method. Among them, in the manufacturing method (1), it is preferable to lift the semiconductor wafer 913 with the protective film-forming film from the side of the supporting sheet 10 across the supporting sheet 10 and lift it up with a pin. FIG. 4D further shows a situation in which the semiconductor wafer 913 with the protective film forming film is pulled away in the direction of arrow P using a pulling means 7 such as a vacuum collet.

When pins are used, the number of pins may be only one, or a plurality of two or more pins. Picking up the semiconductor wafer 913 with the protective film forming film is preferably performed at normal temperature, but may also be performed at room temperature.

With the E'(2) of the first test piece produced from the protective film-forming film 13 being 200 MPa or more, the protective film-forming film 130 after the pickup step (more specifically, the second test piece of the protective film-forming film 130 On the surface 130b), it is possible to suppress the residue of the push-up mark of the pin.

＜Joining step＞ Manufacturing method (1) After the foregoing pickup step, in the foregoing bonding step, as shown in FIG. 4E , the protruding electrodes in the picked up semiconductor wafer 913 with a protective film forming film are flip-chip connected to the substrate 6 The circuit surface 6a is connected to the circuit surface 6a, and the semiconductor chip 913 with the protective film forming film is bonded to the circuit surface 6a. The protruding electrodes are provided on the circuit surface 90a of the semiconductor wafer 90 in the semiconductor wafer 913 with the protective film forming film. In the bonding step, for example, the protruding electrodes in the semiconductor wafer 913 with the protective film forming film are brought into contact with the connection pads provided on the circuit surface 6a of the substrate 6, so that the protruding electrodes are connected to the circuit surface 6a. The aforementioned connection pads on the substrate generate electrical connections and enable flip-chip connections. In the substrate 6 shown in FIG. 4E , illustrations of circuits and the like are omitted. The semiconductor wafer 913 with the protective film forming film can be bonded to the circuit surface 6a by a known method.

＜Thermal hardening step＞ After the aforementioned bonding step in the manufacturing method (1), in the aforementioned thermal hardening step, by thermally curing the protective film forming film 130 in the semiconductor wafer 913 with the protective film forming film, as shown in FIG. 4F, a protective film is formed. Membrane 130'. Thereby, the semiconductor wafer 913 with the protective film forming film becomes the semiconductor wafer with a protective film 913', which includes the semiconductor wafer 90 and the protective film 130' provided on the inner surface 90b of the semiconductor wafer 90. In FIG. 4F, symbol 130b' indicates the second surface of the protective film 130', and corresponds to the second surface 130b of the protective film forming film 130 after cutting.

In the thermal hardening step, the heating temperature and heating time when thermally curing the protective film forming film 130 are as described above.

When the E'(3) of the second test piece made of the protective film-forming film 13 is 500 MPa or more, the protective film 130' will have high protective performance, and the protective effect of the semiconductor wafer 90 will be high. Furthermore, since the E'(2) of the first test piece produced from the protective film-forming film 13 is 200 MPa or more, the protective film-forming film 13 (more specifically, the first test piece of the protective film-forming film 13) is modified in the printing step. The printing performed on the second side 13b) can be clearly retained on the protective film 130' (more specifically, the second side 130b' of the protective film 130').

In the manufacturing method (1), the substrate 6 having the semiconductor wafer 913' with the protective film obtained by the thermal hardening step is used. Next, a semiconductor package is manufactured according to a known method, and by using this Semiconductor packages can be used to manufacture target semiconductor devices.

So far, as the manufacturing method (1), the manufacturing method of a semiconductor device in the case of using the composite sheet for protective film formation has been described. However, even if a protective film forming film that does not constitute the composite sheet for protective film formation is used instead of the protective film forming Semiconductor devices can also be manufactured using composite sheets. 5A to 5G are schematically illustrating an example of the manufacturing method in the case of forming a film using a protective film that does not constitute the composite sheet for forming a protective film in the manufacturing method of the semiconductor device according to the present embodiment (in this specification , sometimes called "manufacturing method (2)") cross-sectional view. Here, a case of using the protective film forming film 13 shown in FIG. 1 will be described.

＜＜Manufacturing method (2)＞＞ ＜Attachment steps＞ In the aforementioned attaching step of the aforementioned manufacturing method (2), as shown in FIG. 5A , the protective film forming film 13 (more specifically, the first peeling film has been removed) that does not constitute the protective film forming composite sheet is The protective film-forming film 13) of 151 is attached to the inner surface 9b of the semiconductor wafer 9 to produce a semiconductor wafer 901 with a protective film-forming film. This step constitutes the protective film forming composite sheet 101. In other words, except that the protective film forming film 13 provided with the second release film 152 is used instead of the protective film forming film 13 provided with the support sheet 10, it is the same as the manufacturing method (1) described above. The attaching steps are the same.

The protective film forming film 13 may also be cut into a circular shape having the same diameter as the semiconductor wafer 9 or a diameter 1 mm to 10 mm smaller than the diameter of the wafer 9 before being attached to the inner surface 9 b of the semiconductor wafer 9 . This improves the workability in the attaching step and the removal workability of the second release film 152 described below.

＜Print steps＞ Manufacturing method (2) After the above-mentioned attaching step, in the above-mentioned printing step, as shown in FIG. 5B , the second release film 152 is newly generated by removing the second release film 152 from the semiconductor wafer 901 to which the protective film forming film is attached. The exposed surface (that is, the second surface 13b of the protective film forming film 13) is irradiated with laser light R, and laser printing is performed on this surface. The semiconductor wafer 901 with a protective film forming film after laser printing is the same as the semiconductor wafer 901 with a protective film forming film after laser printing in the manufacturing method (1). In the manufacturing method (2), the E'(2) of the first test piece manufactured by using the protective film-forming film 13 is 200 MPa or more, and the protective film-forming film 13 (more specifically, the protective film 13 after the printing step) Printing can also be clearly formed on the second surface 13b) of the film forming film 13.

＜Steps for attaching cutting sheet＞ After the aforementioned printing step in the manufacturing method (2), as shown in FIG. 5C , the dicing sheet 80 is attached to the second surface 13 b of the protective film forming film 13 in the semiconductor wafer 901 with the protective film forming film. The dicing sheet 80 includes a base material 81 and an adhesive layer 82 provided on one side of the base material 81 . In this step, the side 82a of the adhesive layer 82 opposite to the side of the substrate 81 (sometimes referred to as the "first side" in this specification) is attached to the second side 13b of the protective film forming film 13 . The first surface 82a of the adhesive layer 82 is the same as the first surface 80a of the cutting blade 80. In this way, the manufacturing method (2) has a step of attaching the dicing sheet to the protective film-forming film in the semiconductor wafer with the protective film-forming film between the printing step and the processing step. The side opposite to the aforementioned semiconductor wafer side is the side.

The cutting sheet 80 may have the same structure as the support sheet 10 in the protective film forming composite sheet 101 . Here, the case where the dicing blade 80 is used is shown. However, in the manufacturing method (2), a known dicing blade other than the dicing blade 80 such as a dicing blade composed only of a base material may be used.

The dicing sheet 80 is attached to the protective film-forming film 13 by a known method. For example, the protective film-forming composite sheet 101 is attached to the semiconductor wafer 9 in the above-described attachment step in the manufacturing method (1). The same method is used for attaching.

In the manufacturing method (2), after the aforementioned dicing sheet attaching step, the semiconductor wafer 901 with the protective film forming film provided with the dicing sheet 80 is used instead of the aforementioned semiconductor wafer with the protective film forming film provided with the supporting sheet 10. Except for the circle 901, the processing step, the picking up step, the bonding step and the thermal hardening step are carried out in the same manner as in the manufacturing method (1), so that the target semiconductor device can be manufactured.

＜Processing steps＞ For example, after the aforementioned printing step (the aforementioned dicing sheet attaching step) in the manufacturing method (2), in the aforementioned processing step, as shown in FIG. 5D , the semiconductor wafer 9 is divided into semiconductors on the dicing sheet 80 wafer 90, and the protective film forming film 13 is cut along the dividing portion of the semiconductor wafer 9 to produce a semiconductor wafer 913 with a protective film forming film. The semiconductor wafer 913 with a protective film forming film obtained in this manner is the same as the semiconductor wafer 913 with a protective film forming film in the manufacturing method (1). In the processing step of the manufacturing method (2), the semiconductor wafer group 903 with a protective film forming film is manufactured together with the semiconductor wafer 913 with a protective film forming film by combining a plurality of semiconductor wafers with a protective film forming film. 913 are arranged neatly on the cutting piece 80.

＜Pickup steps＞ For example, after the aforementioned processing step in the manufacturing method (2), in the aforementioned picking up step, as shown in FIG. 5E , the semiconductor wafer 913 with the protective film forming film is pulled away from the dicing sheet 80 and picked up. In the aforementioned pickup step of the manufacturing method (2), the second surface 130b of the protective film forming film 130 in the semiconductor wafer 913 with the protective film forming film and the first surface 82a of the adhesive layer 82 in the dicing sheet 80 are Peeling occurs between them. In the manufacturing method (2), the E'(2) of the first test piece manufactured by using the protective film-forming film 13 is 200 MPa or more, and the protective film-forming film 130 (more specifically, the protective film 130 after the pickup step) In the second surface 130b) of the film forming film 130, it is also possible to suppress the lifting marks of the remaining pins.

<Joining step, thermal hardening step> The semiconductor wafer 913 with the protective film forming film picked up in the aforementioned pickup step of the manufacturing method (2) is the same as the semiconductor wafer 913 with the protective film forming film picked up in the aforementioned pickup step of the manufacturing method (1). . Therefore, the aforementioned bonding steps and thermal hardening steps in the manufacturing method (2), as shown in FIGS. 5F to 5G , are also the same as the aforementioned bonding steps and thermal hardening steps in the manufacturing method (1). In the manufacturing method (2), the E'(3) of the second test piece manufactured by using the protective film forming film 13 is 500 MPa or more, the protective film 130' also has high protective performance, and the protective effect of the semiconductor wafer 90 is Also high. Furthermore, in the manufacturing method (2), the E'(2) of the first test piece manufactured by using the protective film-forming film 13 is 200 MPa or more, and in the printing step, the protective film-forming film 13 (more specifically, The printing performed on the second side 13b) of the protective film forming film 13 is also clearly retained on the protective film 130' (more specifically, the second side 130b' of the protective film 130').

＜＜Modification of the method of manufacturing a semiconductor device＞＞ The manufacturing method of the semiconductor device of this embodiment may also include steps that are not equivalent to the aforementioned attaching step, the aforementioned printing step, the aforementioned dicing sheet attaching step, the aforementioned processing step, and the aforementioned picking-up step within the scope that does not impair the effects of the present invention. , other steps of any one of the aforementioned bonding step and the aforementioned thermal hardening step. The aforementioned other steps can be selected arbitrarily according to the purpose and are not particularly limited. The time point for performing the aforementioned other steps can be appropriately selected based on the content of the aforementioned other steps.

As an example of the aforementioned other steps in the manufacturing method of the aforementioned semiconductor device, there can be cited: a back polishing tape attaching step, in which the back grinding tape is attached to the circuit surface of the semiconductor wafer before the aforementioned attaching step; and The back polishing tape removal step is to remove the back polishing tape from the circuit surface of the semiconductor wafer between after and before the aforementioned back polishing tape attaching step. The back polishing tape may also be a known back polishing tape, and the attachment of the back polishing tape to the circuit surface of the semiconductor wafer and its removal from the circuit surface of the semiconductor wafer can be performed by known methods.

In this specification, only "attaching step" means that it does not belong to any of the "cutting sheet attaching step" and "back polishing tape attaching step", and means that the aforementioned protective film is formed into a film or the aforementioned protective film The protective film in the composite sheet is formed to be attached to the inner surface of the semiconductor wafer in the aforementioned step.

So far, as the manufacturing method (1), the case of using the protective film forming composite sheet 101 as shown in FIG. 2 has been described. However, in the manufacturing method of the semiconductor device of this embodiment, the method as shown in FIG. 3 can also be used. The composite sheet 102 for forming a protective film shown is mainly other composite sheets for forming a protective film. When the other composite sheet for protective film formation is used, the semiconductor of this embodiment may also be used based on the structural difference between the other composite sheet for protective film formation and the composite sheet for protective film formation 101 shown in FIG. 2 . The method of fabricating the device may also have other steps described above performed at any point in time. [Example]

Below, the present invention will be described in further detail with specific examples. However, the present invention is not limited to the embodiments shown below.

＜Making raw materials for resin＞ The formal names of the manufacturing raw materials, which are abbreviated as resins in the present Examples and Comparative Examples, are as follows. MA: Methyl acrylate HEA: 2-hydroxyethyl acrylate ACrMO: 4-acrylylmorpholine

＜Making raw materials of composition for forming protective film＞ The raw materials used for manufacturing the protective film forming composition are shown below. [Polymer component (A)] (A)-1: Acrylic polymer (weight average molecular weight 400000, glass transition temperature 6°C) copolymerized MA (85 parts by mass) and HEA (15 parts by mass) (A)-2: Acrylic polymer (weight average molecular weight 200000, glass transition temperature 29°C) copolymerized MA (60 parts by mass), ACrMO (25 parts by mass) and HEA (15 parts by mass) [Epoxy resin (B1)] (B1)-1: Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 g/eq to 194g/eq) [Thermal hardener (B2)] (B2)-1: Dicyanodiamide (heat-active latent epoxy resin hardener, "DICY7" manufactured by Mitsubishi Chemical Corporation) [Harding accelerator (C)] (C)-1: Imidazole hardening accelerator (1,3,5-triazine-2,4,6(1H,3H,5H)-trione and 6-2-(2-methyl-1H-imidazole) -1:1 mixture of 1-yl)ethyl-1,3,5-triazine-2,4-diamine, "CUREZOL (registered trademark) 2MAOK-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) (C)-2: 2-phenyl-4,5-dihydroxymethylimidazole ("CUREZOL (registered trademark) 2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.) (C)-3: 2-Undecylimidazole ("CUREZOL (registered trademark) C11Z" manufactured by Shikoku Chemical Industry Co., Ltd.) [Filling material (D)] (D)-1: Silica filler ("SC105G-MMQ" manufactured by Admatechs, spherical silica filler surface-modified with vinyl, average particle size 0.3 μm) [Color(I)] (I)-1: Organic black pigment ("6377 Black" manufactured by Dainichi Seika Industrial Co., Ltd.)

[Example 1] ＜＜Production of protective film forming film＞＞ <Production of protective film forming composition (III)> By combining polymer component (A)-1 (25.9 parts by mass), epoxy resin (B1)-1 (10 parts by mass), hardening accelerator (C)-1 (1.1 parts by mass), and filler (D) -1 (60 parts by mass) and coloring agent (I)-1 (3 parts by mass) are dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C, so that the total concentration of all components except the solvent is 60 Mass % of the composition (III)-1 for forming a thermosetting protective film. The mixing amounts of components other than methyl ethyl ketone shown here are the mixing amounts of the target product excluding the solvent.

＜Manufacture of protective film forming film＞ A release film (second release film, "SP-PET502150" manufactured by Lintec Co., Ltd., thickness 50 μm) in which one side of the polyethylene terephthalate film was peeled off with polysiloxane treatment was used. The protective film-forming composition (III)-1 obtained above was applied to the peeling-treated surface and dried at 100° C. for two minutes to produce a thermosetting protective film-forming film with a thickness of 25 μm.

Furthermore, under the conditions of attachment speed of 2 m/min, attachment temperature of 60°C, and attachment pressure of 0.5 MPa, the release film (first release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm ) is attached to the exposed surface on the side without the second release film of the obtained protective film-forming film, and a protective film-forming film with a release film is produced by having a protective film-forming film, The protective film-forming film is composed of a first release film on one side and a second release film provided on the other side of the protective film-forming film.

＜＜Evaluation of protective film forming film＞＞ <Measurement of the minimum value E’(1) and the maximum value E’(2) of the storage elastic modulus E’ of the first test piece> It is produced by using the eight pieces of protective film-forming films with release films obtained as above and sequentially bonding the exposed surfaces of the protective film-forming films while removing the first release film or the second release film. A laminate composed of a second release film, eight protective film-forming films (total thickness: 200 μm), and a second release film laminated in this order. Next, slices with a width of 4 mm and a length of 30 mm were cut out from the laminate. Next, the two outermost pieces of the second release film were removed from the slice, and the resultant was used as a first test piece. Next, a dynamic viscoelasticity measuring device ("Rheovibron DDV-II-EP1" manufactured by ORIENTEC Co., LTD) was used to perform the stretching method (tensile mode) at a distance of 20 mm between the chucks, a frequency of 11 Hz, and a temperature rise rate of 3°. The storage elastic modulus E' of the first test piece was measured under the measurement conditions of C/min and constant temperature rise in the temperature range from −20°C to 150°C. Among them, the minimum value E’(1) and the maximum value E’(2) in the temperature range of 23°C to 70°C are shown in Table 1.

＜＜Evaluation of protective film forming film＞＞ <Measurement of the minimum value E’(3) of the storage elastic modulus E’ of the second test piece> In the same manner as described above, a laminate in which the second release film, eight protective film-forming films (total thickness: 200 μm), and the second release film were sequentially laminated was produced. Next, a slice having a width of 5 mm and a length of 30 mm was cut out from the laminate. This slice was heat-hardened by heating at 180°C for five minutes, and the two outermost second release films were removed from the heat-hardened slice, and the resultant was used as a second test piece. Then, a dynamic viscoelasticity measuring device ("DMA Q800" manufactured by TA Instruments) was used, using the stretching method (tensile mode), with a distance between the chucks of 20 mm, a frequency of 11 Hz, a heating rate of 3°C/min, and a constant velocity. Under the temperature rising measurement conditions, the storage elastic modulus E' of the second test piece was measured in the temperature range from −60°C to 350°C. Among them, the minimum value E’(3) in the temperature range of 23°C to 70°C is shown in Table 1.

<Evaluation of the adhesion of protective film forming films to semiconductor wafers> A film laminator ("FIRST LAMINATOR VA-400" manufactured by Daesung Laminator Co., Ltd.) is used, with a rubber roller heated to 70°C, and under the conditions of a bonding speed of 0.3m/min and a bonding pressure of 0.3MPa. Next, the protective film-forming film obtained above was attached to the #2000 polished surface of a 6-inch silicon wafer (thickness: 350 μm) to produce a silicon wafer with a protective film-forming film. The attaching temperature of the protective film forming film is 70°C. The adhesion of the protective film forming film to the silicon wafer at this time was evaluated based on the following criteria. The results are shown in Table 1. (evaluation criteria) A: After cooling, the protective film-forming film is not peeled off from the silicon wafer but closely adheres to the silicon wafer. The protective film-forming film has excellent adhesion to the silicon wafer. B: At least part of the protective film-forming film is peeled off from the silicon wafer after cooling, and the protective film-forming film has poor adhesion to the silicon wafer.

＜Evaluation on the retention of printing on the protective film＞ The surface (exposed surface) of the protective film-forming film in the silicon wafer with the protective film-forming film obtained as above that is opposite to the silicon wafer side is printed using a laser printing device (Io Technology Co., Ltd. ("CSM300M" manufactured by EO Technics Co., Ltd.) is directly irradiated with laser light at room temperature (at a temperature of 23°C) to perform laser printing on the aforementioned surface. At this time, set the wavelength of the laser light to 532nm, set the frequency of the laser light to 40kHz, set the scanning speed to 300mm/s, and print the text sequence "ABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789". Set the text size to 0.3mm x 0.2mm per word. Next, the silicon wafer with the protective film-forming film after laser printing is heated at 180° C. for five minutes, so that the protective film-forming film is thermally hardened to form a protective film. The printing (letters) on the protective film derived from the protective film-forming film was visually observed, and the printing retention of the protective film was evaluated based on the following criteria. The results are shown in Table 1. (evaluation criteria) A: The printing is clear and can be easily recognized, and the printing on the protective film has high retention. B: The printing is slightly blurred and cannot be easily recognized, and the retention of the printing on the protective film is low. C: The printing is not clear and cannot be read, and the retention of the printing on the protective film is very low.

＜Evaluation of the residual inhibitory effect of pin lift marks on the protective film forming film＞ A silicon wafer with a protective film forming film was produced in the same manner as in the above "Evaluation of Adhesion of Protective Film Forming Film to Semiconductor Wafer". Next, by attaching a dicing piece ("Adwill D-676H" manufactured by Lintec Corporation) to the silicon wafer with the protective film forming film, the side of the protective film forming film opposite to the silicon wafer side is The surface (exposed surface) is used to manufacture a laminate of a dicing sheet and a silicon wafer with a protective film forming film. Next, a cutting device ("DFD6362" manufactured by DISCO) and a cutting blade (ZH05-SD2000-N1-90CC) were used, and the conditions were that the cutting blade moving speed was 50 mm/s, the cutting blade rotation speed was 30000 rpm, and the blade height was 60 μm. Next, the silicon wafer and the protective film-forming film in the laminate obtained as above are cut. A silicon wafer group with a protective film-forming film is thus manufactured, which includes a silicon wafer with a size of 5 mm × 5 mm (thickness 350 μm) and a protective film of the same size (2 mm × 5 mm) provided on the #2000 grinding surface of the silicon wafer. A plurality of silicon wafers with protective film-forming films to form a film (thickness 25 μm) are arranged neatly on the dicing sheet and are in a fixed state.

Next, from the outside of the diced piece side of the silicon wafer group with the protective film-forming film, the diced piece was irradiated with ultraviolet light of a wavelength of 365 nm under the conditions of illumination intensity of 230 mW/cm ² and light intensity of 190 mJ/cm ² . Next, by using a die bonding machine ("BESTEM-D510" manufactured by Canon Machinery Co., Ltd.) at room temperature (under a temperature condition of 23°C), the silicon wafer with the protective film-forming film is removed from the silicon wafer with a pin. The side of the cutting blade is lifted up across the cutting blade, and five silicon wafers with protective film-forming films are sequentially picked up from the cutting blade after being irradiated with ultraviolet rays. At this time, a pin having a curvature radius of 250 μm at the tip of the protruding portion was used as the pin.

Next, the exposed surfaces of the protective film-forming films (the surfaces where the dicing sheets were originally attached) among the five picked-up silicon wafers with protective film-forming films were visually observed, and further observed using an optical microscope. Based on the following As a benchmark, the residual suppression effect of pin lift marks on the protective film forming film is evaluated. The results are shown in Table 1. (evaluation criteria) A: Both visual observation and observation using an optical microscope showed that no pin popping marks were observed, and the protective film forming film has a high residual inhibition effect on pin popping marks. B: Although the pin lifting marks were not confirmed by visual observation, however, in the observation using an optical microscope, the pin lifting marks were confirmed, and the residual suppression effect of the pin lifting marks on the protective film-forming film was poor. In A. C: The pin lifting marks were confirmed both by visual observation and observation using an optical microscope, and the residual suppression effect of the pin lifting marks on the protective film forming film was low.

<Evaluation of protective performance of protective film> In the same manner as above, a laminate in which the second release film, eight protective film-forming films (total thickness: 200 μm), and the second release film were laminated in this order was produced. Next, the laminate was heated at 180° C. for five minutes, thereby thermally curing all the protective film-forming films in the laminate. Next, slices of 10 mm×10 mm were cut out from the heated laminate (after the protective film-forming film was thermally cured). The result obtained by removing the two outermost second release films from this section was used as a third test piece. Ten third test pieces were prepared. Next, a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation) was used, and a wedge-shaped anti-bending jig with a width of 4 mm was used. The distance between the supporting points was 6 mm and the speed of the anti-bending jig was 0.01 m/min. The three-point bending flexural strength of ten third test pieces was measured, and the average value was used as the flexural strength of the protective film. Furthermore, the stress was calculated by dividing the flexural strength by the cross-sectional area of the third test piece, and based on this stress, the protective performance of the protective film was evaluated based on the following criteria. The results are shown in Table 1. (Evaluation criteria) A: The stress is 15mN/mm2 ^or more, and the protective film has high protective performance. B: The stress is 6mN/mm ² or more and less than 15mN/mm ² , and the protective performance of the protective film is worse than A. C: The stress is less than 6mN/mm ² , and the protective performance of the protective film is low.

＜＜Manufacturing and Evaluation of Protective Film Forming Film＞＞ [Example 2] By combining polymer component (A)-2 (25.9 parts by mass), epoxy resin (B1)-1 (10 parts by mass), thermosetting agent (B2)-1 (0.55 parts by mass), and hardening accelerator (C )-2 (0.55 parts by mass), filler (D)-1 (60 parts by mass), and colorant (I)-1 (3 parts by mass) are dissolved or dispersed in methyl ethyl ketone, and at 23°C Stirring was performed to obtain a thermosetting protective film-forming composition (III)-2 in which the total concentration of all components except the solvent was 60 mass %. The mixing amounts of components other than methyl ethyl ketone shown here are the mixing amounts of the target product excluding the solvent.

A protective film-forming film was produced in the same manner as in Example 1 except that the protective film-forming composition (III)-2 obtained above was used instead of the protective film-forming composition (III)-1. Make an evaluation. The results are shown in Table 1.

[Example 3, Comparative Examples 1 to 3] The protective film-forming film was produced in the same manner as in Example 1 except that either or both of the types and amounts of the mixed components were changed so that the components and contents of the protective film-forming film were as shown in Table 1. Protective films were formed and evaluated. The results are shown in Table 1.

[Table 1]

From the above results, it can be seen that in Examples 1 to 3, when the silicon wafer with the protective film forming film is picked up by lifting the pin, the residue of the lifting mark of the pin on the protective film forming film is suppressed. High efficacy. In addition, in Examples 1 to 3, when the protective film is formed, the printing retention on the protective film is high. In Examples 1 to 3, E'(2) of the first test piece was 280 MPa or more.

In Examples 1 to 3, the protective film-forming film has excellent adhesion to the semiconductor wafer. In Examples 1 to 3, E'(1) of the first test piece was 40 MPa or less.

In Example 1 to Example 3, the protective performance of the protective film is high. In Examples 1 to 3, E'(3) of the second test piece was 5402 MPa or more.

On the other hand, in Comparative Example 1, the print retention on the protective film was significantly low, and the residual suppression effect of the pin kick marks on the protective film forming film was low. In addition, in Comparative Example 1, the protective performance of the protective film was also slightly poor. In Comparative Example 1, both E'(2) of the first test piece and E'(3) of the second test piece were low.

In Comparative Example 2, the protective film-forming film had poor adhesion to the semiconductor wafer. In Comparative Example 2, the first test piece has a high E'(1).

In Comparative Example 3, the print retention on the protective film was significantly low, and the residual inhibitory effect on the push-up marks of the pins on the protective film-forming film was low. In addition, in Comparative Example 3, the protective performance of the protective film was also low. In Comparative Example 3, both E'(2) of the first test piece and E'(3) of the second test piece were low. [Industrial Availability]

The present invention can be used to manufacture semiconductor devices.

6:Substrate 6a: Circuit surface of substrate 7: Separate means 9:Semiconductor wafer 9a: Circuit surface of semiconductor wafer 9b: Inner surface of semiconductor wafer 10:Support piece 10a: One side of the support piece (first side) 11:Substrate 11a: Side 1 12: Adhesive layer 12a: Side 1 13,23: Protective film forming film 13a, 23a: The side where the protective film forms the film (first side) 13b, 23b: The surface of the protective film forming film located on the support sheet side (second surface) 15: Peel off film 16: Adhesive layer for fixtures 16a: Side 1 80: Cutting piece 80a: Side 1 81:Substrate 82: Adhesive layer 82a: Side 1 90:Semiconductor wafer 90a: Circuit surface 90b:Inner surface 101,102: Composite sheet for protective film formation 130: Protective film forming film 130’:Protective film 130a: Side 1 130b:Second side 130b’: Second side 151: First peeling film 152:Second peeling film 901: Semiconductor wafer with protective film forming film 902: Semiconductor wafer group with protective film forming film 913: Semiconductor wafer with protective film forming film 913’: Semiconductor chip with protective film P:arrow R: laser light

[Fig. 1] is a cross-sectional view schematically showing an example of a protective film-forming film according to an embodiment of the present invention. [Fig. 2] is a cross-sectional view schematically showing an example of the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 3] is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 4A] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4B] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4C] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4D] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4E] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4F] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [FIG. 5A] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5B] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5C] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5D] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [FIG. 5E] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5F] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [FIG. 5G] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention.

13: Protective film forming film

13a: The side where the protective film forms the film (first side)

13b: The surface of the protective film forming film located on the support sheet side (second surface)

151: First peeling film

152:Second peeling film

Claims (6)

A protective film-forming film that is thermosetting; A first test piece with a width of 4 mm, which is a laminate of plural pieces of the protective film-forming film, was held at two places with an interval of 20 mm, and was operated in a tensile mode at a frequency of 11 Hz and a temperature rise rate of 3°C/min. Under the condition of constant temperature rise, while the temperature of the first test piece is raised from −20°C to 150°C, the storage elastic modulus E′ of the first test piece is measured at 23°C to 70°C. The minimum value E'(1) of the aforementioned storage elastic modulus E' in the temperature range of °C is below 45MPa, and the maximum value of the aforementioned storage elastic modulus E' in the temperature range of 23°C to 70°C E'(2) is above 200MPa; Furthermore, a second test piece with a width of 5 mm, which was obtained by thermally curing a plurality of laminates of the protective film-forming films, was held at two places with an interval of 20 mm, and the temperature was raised in a tensile mode at a frequency of 11 Hz. When the storage elastic modulus E' of the second test piece is measured while heating the second test piece from −60°C to 350°C at a constant temperature rise rate of 3°C/min, The minimum value E'(3) of the aforementioned storage elastic modulus E' in the temperature range of 23°C to 70°C is more than 500MPa. The protective film-forming film according to claim 1, wherein the protective film-forming film contains a hardening accelerator (C). The protective film-forming film according to claim 1 or 2, wherein the protective film-forming film is a single layer. A composite sheet for forming a protective film, which has: support piece; and The protective film forming film is arranged on one surface of the aforementioned supporting sheet; The aforementioned protective film-forming film is the protective film-forming film described in any one of claims 1 to 3. A manufacturing method of a semiconductor device, the manufacturing method has the following steps: The attaching step is to attach one side of the protective film-forming film as described in any one of claims 1 to 3 or the exposed surface of the protective film-forming film of the protective film-forming composite sheet as described in claim 4. Attached to the inner surface of the semiconductor wafer; The printing step is to perform laser printing on the surface of the protective film-forming film in the protective film-forming composite sheet that is located on the side of the supporting sheet after the above-mentioned attaching step, when the aforementioned protective film-forming composite sheet is used. , when using the protective film-forming film that does not constitute the protective film-forming composite sheet, perform laser printing on the other side of the protective film-forming film; The processing step is to divide the semiconductor wafer into semiconductor wafers on the supporting sheet in the protective film forming composite sheet after the printing step, and separate the semiconductor wafers along the The protective film-forming film is cut at the division point of the semiconductor wafer, and when the protective film-forming film that does not constitute the protective film-forming composite sheet is used, the cutting piece is attached to another part of the protective film-forming film. After one side, the semiconductor wafer is divided into semiconductor wafers on the dicing sheet, and the protective film forming film is cut along the dividing parts of the semiconductor wafer to produce a semiconductor wafer with a protective film forming film, which has The aforementioned semiconductor wafer, and the cut aforementioned protective film-forming film provided on the inner surface of the aforementioned semiconductor wafer; The picking-up step is to pull the semiconductor wafer with the protective film-forming film away from the aforementioned cutting piece or supporting piece after the aforementioned processing step and pick it up; The bonding step is to flip-chip bond the protruding electrodes in the picked-up semiconductor wafer with the protective film-forming film to the circuit surface of the substrate after the aforementioned picking-up step, so that the aforementioned protective film-forming film is attached to the semiconductor wafer. The semiconductor chip is bonded to the aforementioned circuit surface; and The thermal hardening step is to form a protective film by thermally curing the protective film-forming film in the semiconductor wafer with the protective film-forming film after the bonding step. The use of a protective film-forming film. The protective film-forming film is attached to the inner surface of a semiconductor wafer on the opposite side to the circuit surface, and is formed on the inner surface of a semiconductor wafer obtained by dividing the semiconductor wafer. protective film; The aforementioned protective film-forming film is the protective film-forming film described in any one of claims 1 to 3.

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