KR20200074112A - Method for manufacturing a film for forming a protective film, a composite sheet for forming a protective film, and a semiconductor chip - Google Patents

Abstract

The film 13 for forming a protective film is an energy ray-curable film for forming a protective film, and the adhesive force between the film 13 for forming a protective film and a silicon wafer is 3N/25 mm or more, and ultraviolet rays are formed on the film 13 for forming a protective film. When irradiated with a protective film, the shear strength of the protective film is 10.5 N/3 mm□ or more.

Description

Method for manufacturing a film for forming a protective film, a composite sheet for forming a protective film, and a semiconductor chip

The present invention relates to a film for forming a protective film, a composite sheet for forming a protective film, and a method for manufacturing a semiconductor chip.

This application claims priority based on Japanese Patent Application No. 2017-208432 for which it applied to Japan on October 27, 2017, and uses the content here.

In recent years, manufacture of a semiconductor device to which a mounting method called a so-called face down method is applied has been performed. In the face down method, a semiconductor chip having an electrode such as a bump is used on the circuit surface, and the electrode is joined to the substrate. For this reason, the back surface on the opposite side to the circuit surface of the semiconductor chip can be exposed.

On the back surface of the exposed semiconductor chip, a resin film containing an organic material is formed as a protective film, and can be introduced into a semiconductor device as a semiconductor chip on which a protective film is formed.

The protective film is used to prevent cracking in the semiconductor chip after the dicing process or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film comprising a film for forming a protective film for forming a protective film on a support sheet is used. The protective film-forming film can form a protective film by curing. In addition, the support sheet can be used to fix the semiconductor wafer when the semiconductor wafer having the protective film forming film or the protective film on the back side is divided into semiconductor chips. In addition, the support sheet can also be used as a dicing sheet, and the composite sheet for forming a protective film can also be used as an integrated film for forming a protective film and a dicing sheet.

As such a composite sheet for forming a protective film, a film having a thermosetting protective film forming film that forms a protective film by curing by heating, for example, has been mainly used so far. However, since the heat curing of the film for forming a thermosetting protective film usually requires a long time of about several hours, shortening of the curing time is required. On the other hand, it has been studied to use a film for forming a protective film which is curable (energy ray curable) by irradiation with energy rays such as ultraviolet rays for forming a protective film.

On the other hand, as a method of obtaining a semiconductor chip, a method of dicing a semiconductor wafer using a dicing blade is widely used. In this method, a semiconductor chip is usually obtained by dividing and dividing a semiconductor film having a protective film forming film or a protective film on the back surface with these protective film forming film or protective film dicing blades.

On the other hand, in recent years, various methods of dividing a semiconductor wafer without using a dicing blade have been studied. For example, a laser beam is irradiated to converge to a focal point set inside the semiconductor wafer to form a modified layer inside the semiconductor wafer, and then, the modified layer is formed, and a semiconductor wafer with a resin film adhered to the back surface is formed. A method of obtaining a semiconductor chip is known by expanding the resin film together with the resin film, cutting the resin film, and dividing and separating the semiconductor wafer at the modified layer site. This method, unlike the method using a dicing blade, does not involve the formation of a cutting portion by a dicing blade in a semiconductor wafer, and the advantage that more semiconductor chips are obtained from the semiconductor wafer and does not generate cutting debris. Have For die-bonding a semiconductor chip to a circuit formation surface of a substrate, there is a film-like adhesive, but the division method has hitherto been mainly used when this film-like adhesive is used as the resin film (Patent Document 1). Reference).

Thus, as the resin film, if the above-described dividing method can be applied to a semiconductor wafer provided with a film for forming an energy ray-curable protective film or a protective film that is a cured product, the method is a semiconductor with a protective film. It is very useful as a method for manufacturing chips.

Japanese Patent Application Publication No. 2012-222002

However, when the film for forming a protective film or a semiconductor wafer provided with a protective film is expanded, the obtained semiconductor chip may peel off from the film or protective film for forming a protective film after cutting. Among them, this problem is remarkable in the peripheral portion of the semiconductor chip, especially in the corner portion.

The present invention includes a protective film forming film or a cured product of the protective film on the back surface, and expands a semiconductor wafer having a modified layer formed therein, cuts the film or protective film for forming a protective film, divides the semiconductor wafer, and divides the semiconductor wafer into semiconductor chips. Provided is a film for forming a protective film or a film for forming a protective film capable of suppressing the lifting of a semiconductor chip from the film, a composite sheet for forming a protective film provided with the film for forming a protective film, and a method for manufacturing the semiconductor chip It is aimed at.

In order to solve the above problems, the present invention is an energy ray-curable protective film forming film, the adhesive force between the film for forming a protective film and a silicon wafer measured by the following method is 3N/25 mm or more, and ultraviolet rays are applied to the film for forming a protective film. When irradiated and used as a protective film, a film for forming a protective film having a shear strength of 10.5 N/3 mm or more of the protective film measured by the following method is provided.

Adhesion between protective film forming film and silicon wafer:

After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film was measured from, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer.

Shear strength of the protective film:

After attaching the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet rays under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film, thereby protecting the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film.

In addition, the present invention provides a composite sheet for forming a protective film provided with a support sheet and having the film for forming a protective film on the support sheet.

In addition, the present invention is a process for attaching a film for forming a protective film or a film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer, and irradiating energy rays to the film for forming a protective film after being attached to the semiconductor wafer, A process of forming a protective film, a process of forming a modified layer inside the semiconductor wafer by irradiating laser light through the protective film or a film for forming a protective film to converge to a focus set inside the semiconductor wafer; The semiconductor wafer on which the modified layer is formed is expanded with the protective film or the film for forming a protective film in the direction of the surface of the protective film or the film for forming a protective film, and the film for forming the protective film or the protective film is cut off. Provided is a method of manufacturing a semiconductor chip having a step of dividing the semiconductor wafer in portions to obtain a plurality of semiconductor chips.

According to the present invention, a protective film, which is a film for forming a protective film or a cured product, is provided on the back surface, and a semiconductor wafer having a modified layer formed therein is expanded, and the film or protective film for forming a protective film is cut, and the semiconductor wafer is divided. When a semiconductor chip is used, a film for forming a protective film or a film for forming a protective film capable of suppressing the lifting of a semiconductor chip from the film, a composite sheet for forming a protective film provided with the film for forming a protective film, and a method for manufacturing the semiconductor chip Is provided.

1 is a cross-sectional view schematically showing a film for forming a protective film according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
7 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a film for forming a protective film that does not constitute a composite sheet for forming a protective film is used.
8 is a cross-sectional view schematically illustrating one embodiment of a method for manufacturing a semiconductor chip when a film for forming a protective film that does not constitute a composite sheet for forming a protective film is used.
9 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip in the case of using a film for forming a protective film that does not constitute a composite sheet for forming a protective film.
10 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a composite sheet for forming a protective film in which the film for forming a protective film is previously integrated with a support sheet is used.
11 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a composite sheet for forming a protective film in which a film for forming a protective film is previously integrated with a support sheet is used.
12 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a composite sheet for forming a protective film in which a film for forming a protective film is previously integrated with a support sheet is used.

◇ Protective film forming film

The film for forming a protective film according to an embodiment of the present invention is a film for forming an energy ray-curable protective film, wherein the adhesion between the film for forming a protective film and a silicon wafer measured by the following method is 3N/25 mm or more, and the film for forming a protective film When the ultraviolet ray was irradiated with a protective film, the shear strength of the protective film measured by the following method was 10.5 N/3 mm□ or more.

Adhesion between protective film forming film and silicon wafer:

After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film was measured from, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer.

Shear strength of the protective film:

After attaching the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet rays under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film, thereby protecting the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film.

As another aspect, the film for forming a protective film according to an embodiment of the present invention is an energy ray-curable protective film forming film, wherein the adhesive force between the film for forming a protective film and the silicon wafer when the film for forming a protective film is measured by the following method The protective film is formed by having a property of 3N/25 mm or more and irradiating ultraviolet rays on the film for forming a protective film as a protective film, and having a shear strength of 10.5 N/3 mm□ or more when measured by the following method. The dragon film has.

Adhesion between protective film forming film and silicon wafer:

After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film was measured from, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer.

Shear strength of the protective film:

After attaching the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet rays under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film, thereby protecting the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film.

In the film for forming a protective film according to one aspect of the present invention, when the adhesive strength and shear strength are measured by the above-described method, the adhesive strength is 3N/25 mm or more and the shear strength is 10.5 N/3 mm□ or more. The film for forming a protective film having the same chemical composition as the chemical composition of the film for forming a protective film having properties may be used, and may have a thickness different from the thickness of the film for forming a protective film evaluated by the following method.

Here, the adhesive force between the protective film forming film and the silicon wafer is 3N/25 mm or more, which means that the adhesive force between the protective film forming film having a width of 25 mm and the silicon wafer is 3N. In addition, when the shear strength of the protective film is 10.5 N/3 mm□ or more, it means that the shear strength of the protective film having a width of 3 mm is 10.5 N.

As will be described later, a composite sheet for forming a protective film can be formed by forming the film for forming a protective film on a support sheet.

The film for forming a protective film is cured by irradiation with energy rays to become a protective film. This protective film is for protecting the back surface of the semiconductor wafer or semiconductor chip (the side opposite to the electrode formation surface). The film for forming a protective film is soft, and can be easily attached to the object to be attached.

Since the film for forming a protective film is energy ray curable, a protective film can be formed by curing in a shorter time than a film for forming a thermosetting protective film.

In addition, in this specification, "the film for protective film formation" means what was before hardening, and "the protective film" means that the film for protective film formation was hardened.

In the present invention, the term "energy beam" means having both energy in an electromagnetic wave or charged particle beam, and examples thereof include ultraviolet rays, radiation, and electron beams.

Ultraviolet rays can be irradiated, for example, by using a high pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet source. The electron beam generated by an electron beam accelerator or the like can be irradiated.

In the present invention, "energy ray curability" means the property of curing by irradiating energy rays, and "non-energy ray curability" means a property that does not cure even when irradiated with energy rays.

When the film for forming a protective film is used, the semiconductor wafer having the modified layer formed therein is expanded in the direction of its surface (for example, the back side), thereby dividing the semiconductor wafer in the modified layer region to produce a semiconductor chip. do.

In order to form a modified layer inside the semiconductor wafer, laser light may be irradiated to converge to a focus set inside the semiconductor wafer. Since the strength of the modified layer of the semiconductor wafer is weak, a force is applied to the modified layer inside the semiconductor wafer by expanding the semiconductor wafer on which the modified layer is formed toward the surface of the semiconductor wafer, whereby the semiconductor wafer is divided at the modified layer region. Thus, a plurality of semiconductor chips are obtained.

The laser light irradiated when forming the modified layer on the semiconductor wafer is preferably a laser light in the infrared region, more preferably a laser light having a wavelength of 1342 nm.

The adhesive strength between the film for forming a protective film and the silicon wafer measured by the method is 3N/25 mm or more, and the shear strength of the protective film measured by the method becomes 10.5 N/3 mm□ or more, thereby providing a semiconductor with a protective film on the back surface. A wafer (sometimes referred to as a "semiconductor wafer with a protective film" in this specification) is expanded, a protective film is cut, and a semiconductor wafer is divided into semiconductor chips (in this specification, a "semiconductor with a protective film formed") Chip” may be suppressed. The lifting of the semiconductor chip from the protective film can be suppressed. The same is true for the film for forming a protective film, and a semiconductor wafer (hereinafter referred to as a "semiconductor wafer on which a film for forming a protective film is formed") is provided with a film for forming a protective film on the back surface is expanded to form a protective film. When the semiconductor film is cut and the semiconductor wafer is divided into semiconductor chips (in this specification, sometimes referred to as "a semiconductor chip on which a film for forming a protective film is formed"), the semiconductor chip from the film for forming a protective film is used. Lifting can be suppressed.

The adhesive force is preferably 3.3 N/25 mm or more, and more preferably 3.6 N/25 mm or more. When the said adhesive force is more than the said lower limit, the effect of suppressing the floating of a semiconductor chip (but not limited to a silicon chip) from the above-mentioned protective film or film for forming a protective film becomes higher.

Meanwhile, the upper limit of the adhesive force is not particularly limited. However, in the method of manufacturing a semiconductor device described later, the adhesive force is preferably 10 N/25 mm or less, and is 9 N/25 mm or less in that the pickup of the semiconductor chip with the protective film or the semiconductor chip with the film for forming the protective film becomes easier. It is more preferably less than or equal to mm, and particularly preferably less than or equal to 8 N/25 mm.

The adhesive force may be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, the adhesive force is preferably 3 to 10 N/25 mm, more preferably 3.3 to 9 N/25 mm, particularly preferably 3.6 to 8 N/25 mm, but these are examples.

The adhesive force can be adjusted, for example, by controlling the type and content of the components of the protective film forming film described later, and the thickness of the protective film forming film. In particular, by adjusting the content of the compound (p), which will be described later, in the film for forming a protective film, the adhesive force can be easily adjusted.

The shear strength is preferably 10.7 N/3 mm□ or more, and more preferably 11.0 N/3 mm□ or more. When the shear strength is equal to or greater than the lower limit, the effect of suppressing the lifting of the semiconductor chip from the above-described protective film or film for forming a protective film is further enhanced.

On the other hand, the upper limit of the shear strength is not particularly limited, for example, preferably 30.0 N/3 mm□ or less, more preferably 27.5 N/3 mm□ or less, and particularly preferably 25.0 N/3 mm□ or less. Do.

The shear strength may be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, the shear strength is preferably 10.5 to 30.0 N/3 mm□, more preferably 10.7 to 27.5 N/3 mm□, particularly preferably 11.0 to 25.0 N/3 mm□, but these are examples. to be.

The shear strength can be adjusted, for example, by adjusting the type and content of the components of the protective film forming film described later, and the thickness of the protective film forming film. In particular, by controlling the content of the compound (p) to be described later in the film for forming a protective film, the shear strength can be easily adjusted.

As an example of the film for forming a protective film, preferably, the adhesive strength is 3 to 10 N/25 mm, and the shear strength is 10.5 to 30.0 N/3 mm□; More preferably, the adhesive strength is 3.3 to 9 N/25 mm, and the shear strength is 10.7 to 27.5 N/3 mm□; Particularly preferably, the adhesive strength is 3.6 to 8 N/25 mm, and the shear strength is 11.0 to 25.0 N/3 mm□.

However, the combination of the adhesive force and shear strength shown here is an example.

As the film for forming a protective film that satisfies the conditions of the above-mentioned adhesive strength and shear strength, for example, a compound having a group and a polymerizable group in which a carboxy group or a carboxy group forms a salt in one molecule (in this specification, "compound (p )”, and it is preferable to contain the energy ray-curable component (a) and the compound (p), which will be described later. The film for forming a protective film containing the compound (p) has not been conventionally known.

It is preferable that the energy ray-curable component (a) is uncured, it is preferable to have tackiness, and it is more preferable to have tackiness while being uncured.

Both the film for forming a protective film and the protective film, which is a cured product, transmittance of the laser light (for example, laser light in an infrared region, such as a laser light having a wavelength of 1342 nm) necessary for forming a modified layer of a semiconductor wafer. It is preferable that this is high. Both the protective film-forming film and the protective film usually exhibit the same tendency with respect to light transmittance.

Meanwhile, in the present specification, the transmittance of light is a value measured by a spectrophotometer without using an integrating sphere.

For example, the transmittance of the laser light having a wavelength of 1342 nm (there may be abbreviated as "film transmittance (1342 nm)" in this specification) of the film for forming a protective film is preferably 45% or more, and 50% It is more preferable that it is the above, and it is especially preferable that it is 55% or more. When the film transmittance (1342 nm) is greater than or equal to the above lower limit, in the method for manufacturing a semiconductor chip to be described later, a modified layer can be more easily formed on a semiconductor wafer.

The upper limit of the film transmittance (1342 nm) is not particularly limited, and may be, for example, 100%.

The transmittance of the laser light having a wavelength of 1342 nm of the protective film (in this specification, sometimes referred to as "protective film transmittance (1342 nm)") is preferably 45% or more, more preferably 50% or more, 55 % Or more is particularly preferred. Since the protective film transmittance (1342 nm) is greater than or equal to the above lower limit, in the method of manufacturing a semiconductor chip to be described later, a modified layer can be more easily formed on a semiconductor wafer.

The upper limit of the protective film transmittance (1342 nm) is not particularly limited, and may be, for example, 100%.

The film transmittance (1342 nm) can be adjusted, for example, by controlling the type and content of the components of the film for forming a protective film, and the thickness of the film for forming a protective film.

The transmittance of the protective film (1342 nm) can be adjusted, for example, by controlling the type and content of the components of the protective film and the thickness of the protective film.

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

On the other hand, in this specification, it is not limited to the case of the film for forming a protective film, and "the multiple layers may be the same or different from each other" means "all of the layers may be the same, all of the layers may be different, and only some of the layers" It may be the same.” Also, “the multiple layers are different from each other” means that “at least one of the constituent materials and the thickness of each layer is different from each other”.

The thickness of the film for forming a protective film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the film for forming a protective film is greater than or equal to the above lower limit, a protective film with a higher protective ability can be formed. Moreover, when the thickness of the film for protective film formation is below the said upper limit, it becomes suppressed that it becomes an excessive thickness.

Here, the "thickness of the film for forming a protective film" means the entire thickness of the film for forming a protective film. For example, the thickness of the film for forming a protective film composed of multiple layers is the sum of all layers constituting the film for forming a protective film. Means the thickness of

In addition, "the thickness of the film for forming a protective film" can be measured as follows. The distance between the surface and the back surface of the film for forming a protective film is measured using a contact-type thickness meter for any five points of the film for forming a protective film. The average value of the five measured points is taken as the thickness of the film for forming a protective film.

The thickness of the release film, support sheet, pressure-sensitive adhesive layer, semiconductor wafer, and substrate described later is also measured by the method described above.

Curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the protective film is sufficiently hard to exert its function, and may be appropriately selected depending on the type of the protective film-forming film.

For example, when curing the film for forming a protective film, it is preferable that the illuminance of the energy ray is 4 to 280 Pa/cm 2. In addition, it is preferable that the amount of light of the energy ray during the curing is 3 to 1000 mJ/cm 2.

1 is a cross-sectional view schematically showing a film for forming a protective film according to an embodiment of the present invention. On the other hand, the drawings used in the following description, in order to make the features of the present invention easier to understand, may be enlarged to show a portion that becomes a main part, and the dimensional ratio of each component is not limited to the same as the actual Does not.

The film 13 for forming a protective film shown here is provided with a first release film 151 on one surface thereof (sometimes referred to as "first surface" in this specification) 13a, and the first A second release film 152 is provided on the other surface (otherwise referred to as "second surface" in this specification) 13b) opposite to the surface 13a.

The film 13 for forming a protective film is suitable for storage in a roll shape, for example.

The film 13 for forming a protective film can be formed using the composition for forming a protective film described later.

The film 13 for forming a protective film is energy ray curable, and satisfies the above-mentioned conditions of adhesive strength and shear strength.

Both the first release film 151 and the second release film 152 may be known.

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, peeling force required when peeling from the film 13 for forming a protective film is different from each other. do.

In the protective film forming film 13 shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is affixed to the exposed surface formed by removing either the first release film 151 or the second release film 152. In addition, the exposed surface formed by removing the other of the first release film 151 and the second release film 152 is an abutment surface of the support sheet.

<<Composition for forming a protective film>>

The film for forming a protective film can be formed using a composition for forming a protective film containing the constituent material. For example, a film for forming a protective film can be formed on a target site by coating a composition for forming a protective film on a surface to be formed of the film for forming a protective film and drying as necessary.

In the composition for forming a protective film, the content ratio of components that are not vaporized at normal temperature is usually the same as the content ratio of the components of the film for forming a protective film. In addition, in this specification, "normal temperature" means the temperature which does not specifically cool or heat, ie, the normal temperature, for example, the temperature of 15-25 degreeC, etc. are mentioned.

Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, And a method of using various coaters such as a Meyer bar coater and a kiss coater.

The drying conditions for the protective film-forming composition are not particularly limited, but when the protective film-forming composition contains a solvent to be described later, heating and drying are preferable. The composition for forming a protective film containing a solvent is desirably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes.

<Composition for forming a protective film (IV-1)>

As a composition for forming a protective film, for example, a composition (IV-1) for forming a protective film containing the energy ray-curable component (a) and the compound (p) may be mentioned. The composition for forming a protective film containing the compound (p) has not been conventionally known.

[Compound (p)]

Compound (p) has a carboxyl group (-C(=O)-O-H) or a group in which a carboxyl group forms a salt and a polymerizable group in one molecule.

Examples of the group in which the carboxy group forms a salt include, for example, a group in which a carboxylate anion (-C(=O)-O-) generated by separation of proton (H ⁺ ) from a carboxy group forms a salt together with a cation.

In the composition (IV-1) for forming a protective film and the compound (p) in the film for forming a protective film, the proton may be undissociated (in other words, the carboxyl group is intact) as the carboxy group, and the proton is released, resulting in a carboxylate anion. It may be.

It is presumed that the compound (p) improves the interaction between the film or protective film for forming a protective film and a semiconductor wafer or semiconductor chip by having a carboxy group or a group in which the carboxy group forms a salt. As a result, it is presumed that lifting of the semiconductor chip from the protective film or the film for forming a protective film is suppressed.

In addition, since the compound (p) has a polymerizable group, it is contained in any one of the polymer components in the protective film (by forming a copolymer), and the transition from the protective film to the layer (film) adjacent to the protective film It is presumed to be suppressed. Since the film for forming a protective film finally forms a protective film by curing, the copolymer derived from the compound (p) is stably present in the protective film, so that the effect of suppressing the lifting of the semiconductor chip from the protective film is stably exhibited. I guess.

The compound (p) having a group in which the carboxyl group forms a salt is composed of one or two or more anion moieties and one or two or more cations. The anion portion has one or two or more carboxylate anions per one.

That is, the number of carboxylate anions in one molecule of compound (p) may be one, or two or more.

Similarly, the number of the anion moieties in one molecule of the compound (p) may be one, or two or more, and in the case of two or more, all of these anion moieties may be the same, all may be different, or a part may be the same. That is, only 1 type may be sufficient as the anion part in 1 molecule of compound (p), 2 or more types may be used, and when it is 2 or more types, the combination and ratio of these are not specifically limited.

The carboxylate anion in one molecule of compound (p) may comprise a group in which the carboxyl group forms a salt, or a part of the carboxyl group may constitute a group in which a salt is formed, but usually all of the carboxyl groups constitute a group in which a salt is formed It is preferred.

The valence of the cation in the compound (p) is not particularly limited, and may be 1 (monovalent) or 2 (bivalent) or higher.

The number of cations in one molecule of the compound (p) may be one, or two or more, and when two or more, these cations may be all the same, may be all different, or may be a part of the same. That is, only one type of cation in one molecule of the compound (p) may be used, or two or more types thereof may be used, and when two or more types are used, the combination and proportion thereof are not particularly limited.

The cations in one molecule of the compound (p) may all form a group in which the carboxyl group forms a salt, or a part of the carboxyl group may form a group in which a salt forms a salt, but usually it is preferable that all the carboxyl groups constitute a group in which a salt is formed. Do.

The group in which the carboxyl group in one molecule of the compound (p) forms a salt may be one, or two or more, and when two or more, these groups may be all the same, all may be different, or only some may be the same. That is, the group in which the carboxyl group in one molecule of the compound (p) forms a salt may be one type, or two or more types, and when two or more types, combinations and ratios of these are not particularly limited.

As the compound (p) having a group in which the carboxyl group has a salt, various forms may be mentioned depending on the type and valence of the cation. As such a compound (p), More specifically, it consists of 1 anion part and 1 cation, for example; Consisting of two or more anion moieties and one cation; Consisting of one anion portion and two or more cations; And two or more anion parts and two or more cations.

It is preferable that the compound (p) having a group in which the carboxy group has a salt form is electrically neutral as a whole molecule, that is, the total value of the valence of cations in one molecule of compound (p) and the total value of the valence of anions.

The cation is not particularly limited, and may be either an inorganic cation or an organic cation.

Among the cations, examples of the inorganic cations include alkali metal ions such as lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), and potassium ions (K ⁺ ); Alkaline earth metal ions such as magnesium ion (Mg ²⁺ ), calcium ion (Ca ²⁺ ), and barium ion (Ba ²⁺ ); Typical metal ions such as aluminum ions (Al ³⁺ ), zinc ions (Zn ²⁺ ), and tin ions (Sn ²⁺ , Sn ⁴⁺ ); Transition metal ions such as copper ions (Cu ⁺ , Cu ²⁺ ), iron ions (Fe ²⁺ , Fe ^{3 +} ), manganese ions, and nickel ions; And non-metal ions such as ammonium ions (NH ₄ ⁺ ).

For example, in the case where the cation is a sodium ion, a group in which the carboxy group forms a salt is represented by the formula "-C(=O)-O ^- Na ⁺ ".

Among the cations, examples of the organic cations include cations derived from amine compounds, quaternary ammonium cations, and the like.

As the cation derived from the amine compound, for example, a cation obtained by protonation of a primary amine, a secondary amine, or a tertiary amine is mentioned.

As said quaternary ammonium cation, the cation which 4 monovalent hydrocarbon groups couple|bonded with 1 nitrogen atom is mentioned, for example.

Among the cations, preferred examples of inorganic and organic cations, which are non-metal ions, include, for example, the formula “(Z ¹ ) ₄ N ⁺ (where Z ¹ is a hydrogen atom, an alkyl group or an aryl group, and a plurality of Z ¹ is It may be the same or different from each other, and when two or more Z ¹ is an alkyl group, these alkyl groups may be bonded to each other to form a ring)”.

The group in which the carboxy group formed by such a cation forms a salt is represented by the formula "-C(=O)-O ^- N ⁺ (Z ¹ ) ₄ (where Z ¹ is the same as above)".

In the above formula, a plurality (i.e., four) of Z ¹ may be all the same, may be all different, or may be the same.

The alkyl group in Z ¹ may be either linear, branched or cyclic, or in the case of cyclic, either monocyclic or polycyclic.

The aryl group in Z ¹ may be either monocyclic or polycyclic.

The linear or branched alkyl group in Z ¹ preferably has 1 to 10 carbon atoms, and examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and iso Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1- Methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3- Dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3 -Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3 ,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1 -Propylbutyl group, n-octyl group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2 -Ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4 -Dimethylhexyl group, 5,5-dimethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, nonyl group and decyl group.

The linear or branched alkyl group in Z ¹ may have, for example, any of 1 to 8, 1 to 5, and 1 to 3 carbon atoms, but these are examples.

The cyclic alkyl group in Z ¹ preferably has 3 to 10 carbon atoms, and examples of the alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cycloox. And a til group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, and tricyclodecyl group.

The number of carbon atoms of the cyclic alkyl group in Z ¹ may be, for example, any of 3 to 8 and 3 to 6, but these are examples.

When two or more (i.e., two, three or four) Z ¹ is the alkyl group, these two or more alkyl groups may be mutually bonded to form a ring together with the nitrogen atom to which these alkyl groups are bonded. . The bonding position of two or more alkyl groups in this case is not particularly limited, and the formed ring may be either monocyclic or polycyclic.

The aryl group in Z ¹ preferably has 6 to 20 carbon atoms, and such aryl groups include, for example, a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, and p-. A tolyl group and a xylyl group (also called a dimethylphenyl group) and the like, and one or more hydrogen atoms of these aryl groups are further substituted with these aryl groups or the alkyl groups in Z ¹ . It is preferable that the aryl group having these substituents includes 6 to 20 carbon atoms including the substituent.

The compound (p) may have only a carboxy group in one molecule, may have only a group in which the carboxy group has a salt, or may have a group in which the carboxy group and the carboxy group have a salt.

The number of the carboxyl group and the group in which the carboxyl group forms a salt in one molecule of the compound (p) may be one or two or more.

The total number of carboxyl groups and groups in which the carboxyl group forms a salt in one molecule of the compound (p) is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2.

In the compound (p), the position of the carboxy group and the group in which the carboxy group forms a salt is not particularly limited. For example, in the compound (p) having a chain structure, these groups may be bound to the distal end of the main chain (may be the distal end of the main chain) or may be bound to the non-terminal end. On the other hand, in this specification, "main chain" means that the largest number of atoms constituting the chain skeleton.

In the compound (p), the number of carboxyl groups or groups in which the carboxyl group forms a salt, which is bonded to one atom, may be one, or two or more (for example, when the atom is a carbon atom, 2 to 4).

The polymerizable group in the compound (p) includes, for example, a group having a polymerizable unsaturated bond, and among them, a group having an ethylenically unsaturated bond (also referred to as a double bond or C=C) is preferable.

The number of the polymerizable groups in one molecule of the compound (p) may be one or two or more, but it is preferably 1 to 3, more preferably 1 to 2.

In the compound (p), the position of the polymerizable group is not particularly limited. For example, in the compound (p) having a chain structure, the polymerizable group may be a terminal end of the main chain or a non-terminal end. However, it is usually preferable that the polymerizable group is the terminal portion of the main chain.

It is preferable that the compound (p) has an ester bond in addition to a carboxy group or a group in which the carboxy group forms a salt and a polymerizable group, and a carboxylic acid ester bond (a group represented by the formula "-C(=O)-O-" or a car It is more preferable to have a). By using such a compound (p), the effect of suppressing the lifting of the semiconductor chip from the protective film or the film for forming a protective film is further enhanced.

The number of the ester bonds in one molecule of the compound (p) may be one, or two or more, but it is preferably 1 to 4, and more preferably 1 to 3.

Preferred compounds (p) are, for example, aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl esters (i.e., the hydrogen number of one carboxy group of the aliphatic dicarboxylic acid is (meth)acryloyloxyalkyl group Substituted compound); Aromatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester (ie, a compound in which the hydrogen atom of one carboxy group of the aromatic dicarboxylic acid is substituted with a (meth)acryloyloxyalkyl group); A compound in which the carboxyl group of the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester is substituted with a group in which the aforementioned carboxyl group forms a salt; And a compound in which the carboxyl group of the aromatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester is substituted with a group in which the above-described carboxyl group forms a salt.

The aliphatic dicarboxylic acid means a compound having two carboxy groups, and non-aromatic divalent hydrocarbon groups having a portion other than these carboxy groups being linear, branched or cyclic.

The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms, for example, any one of 2 to 5 and 2 to 4 carbon atoms.

It is preferable that the said hydrocarbon group is an alkylene group.

The aromatic dicarboxylic acid means a compound having two carboxy groups, and sites other than these carboxy groups are divalent aromatic hydrocarbon groups (also called arylene groups).

The aromatic hydrocarbon group may be either monocyclic or polycyclic.

The aromatic hydrocarbon groups include for example, the removal of one hydrogen atom from the aryl group (also referred to as arylene group), a divalent group in Z ^1.

The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.

In the compound in which the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester and its carboxyl group are substituted with a group in which the above-described carboxyl group forms a salt, an alkyl group bonded to a (meth)acryloyloxy group (in other words, , (Meth)alkylene group in the acryloyloxyalkyl group) may be any one of a linear, branched and cyclic, may have a chain structure and a cyclic structure together, but is preferably linear or branched.

The number of carbon atoms of the linear or branched alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 6, for example, 2 to 5 and 2 Any of ∼4 may be used.

The number of carbon atoms of the cyclic alkyl group is not particularly limited, but is preferably 3 to 10, more preferably 4 to 8, and particularly preferably 5 to 6.

It is preferable that the compound (p) has a chain structure, and both the carboxyl group or the group in which the carboxyl group forms a salt and the polymerizable group are the terminal ends of the main chain, and have an ester bond at the non-terminal end of the main chain.

As such a preferable compound (p), an aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester; And a compound wherein the carboxyl group of the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester is substituted with a group in which the above-described carboxyl group forms a salt.

Particularly preferred compound (p) is 1-[2-(acryloyloxy)ethyl succinic acid] (also referred to as mono succinic acid (2-acryloyloxyethyl)) CH ₂ =CH-C(=O)- O-CH ₂ CH ₂ -OC(=O)-CH ₂ CH ₂ -C(=O)-OH); Succinic acid 1-[2-(methacryloyloxy)ethyl](CH ₂ =C(-CH ₃ )-C(=O)-O-CH ₂ CH ₂ -OC(=O)-CH ₂ CH _2- C(=O)-OH); 1-[2-(acryloyloxy)ethyl glutaric acid](CH ₂ =CH-C(=O)-O-CH ₂ CH ₂ -OC(=O)-CH ₂ CH ₂ CH ₂ -C( =O)-OH); A compound in which the carboxyl group of 1-[2-(acryloyloxy)ethyl] succinic acid is substituted with a group in which the aforementioned carboxyl group forms a salt; A compound in which the carboxyl group of 1-[2-(methacryloyloxy)ethyl] succinic acid is substituted with a group in which the aforementioned carboxyl group forms a salt; And a compound in which the carboxyl group of 1-[2-(acryloyloxy)ethyl glutaric acid] is substituted with a group in which the above-described carboxyl group forms a salt.

The molecular weight (absolute molecular weight) of the compound (p) is not particularly limited, but is preferably 100 to 1000, more preferably 100 to 700, further preferably 100 to 500, and particularly preferably 100 to 300. .

The composition (IV-1) for forming a protective film and the compound (p) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the composition for forming a protective film (IV-1), the ratio of the content of the compound (p) to the total content of components other than the solvent (that is, the content of the compound (p) in the film for forming a protective film, in other words, the film for forming a protective film) The mass of the compound (p) relative to the total mass of) is preferably 0.15 mass% or more, more preferably 0.2 mass% or more, and particularly preferably 0.25 mass% or more. When the said content ratio is more than the said lower limit, the effect of suppressing the floating of a semiconductor chip from a protective film or a film for forming a protective film becomes higher.

In addition, the upper limit of the said content ratio (content of the compound (p) of the film for protective film formation) is not specifically limited. However, it is preferable that the content ratio is 3% by mass or less in view of the effect of excessive use of the compound (p), and as a result, the degree of hardening of the protective film is further enhanced and the properties of the protective film are further improved. It is more preferable that it is mass% or less, and it is especially preferable that it is 1 mass% or less.

The content ratio (the content of the compound (p) in the film for forming a protective film) can be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, the content ratio is preferably 0.15 to 3% by mass, more preferably 0.2 to 2% by mass, particularly preferably 0.25 to 1% by mass, but these are examples.

[Energy ray curable component (a)]

The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film forming properties, flexibility, and the like to the film for forming a protective film.

The energy ray-curable component (a) is, for example, a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000, and an absolute molecular weight or a weight average molecular weight having an energy ray-curable group having 100 to 80000 And compound (a2). The polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may be crosslinked.

In addition, in this specification, a weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC) method, unless otherwise specified.

(A polymer having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000 (a1))

As the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000, for example, an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and a group reacting with the functional group and energy ray-curable And an acrylic resin (a1-1) formed by polymerization of an energy ray-curable compound (a12) having an energy ray-curable group such as a double bond.

Examples of the functional groups capable of reacting with groups of other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (groups in which one or two hydrogen atoms of an amino group are substituted with groups other than hydrogen atoms), epoxy groups, and the like. . However, from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip, the functional group is preferably a group other than a carboxy group.

Among these, it is preferable that the said functional group is a hydroxyl group.

・Acrylic polymer having a functional group (a11)

Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerizing an acrylic monomer having the functional group with an acrylic monomer having no functional group, and in addition to these monomers, monomers other than the acrylic monomer ( The non-acrylic monomer) may be copolymerized.

Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

Examples of the hydroxyl group-containing monomer include (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, and (meth) (Meth)acrylic acid hydroxyalkyl, such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; And non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols having no (meth)acryloyl skeleton).

In addition, in this specification, "(meth)acrylic acid" means the concept including both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid.

Examples of the carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid (monocarboxylic acids having ethylenically unsaturated bonds); Ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid (ie, dicarboxylic acids having ethylenically unsaturated bonds); Anhydride of the ethylenically unsaturated dicarboxylic acid; And (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

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

As for the acrylic monomer which comprises the said functional group which comprises the said acrylic polymer (a11), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

Examples of the acrylic monomer having no functional group include (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)isopropyl acrylate, (meth)n-butyl acrylate, (meth) )Isobutyl acrylate, (meth)acrylic acid sec-butyl, (meth)acrylic acid tert-butyl, (meth)pentyl acrylate, (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid 2-ethylhexyl, (meth) )Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (( (Meta) acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl (also called (meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)) Alkyl groups constituting alkyl esters such as palmityl acrylate), (meth)acrylic acid heptadecyl and (meth)acrylic acid octadecyl (also called (meth)acrylic acid stearyl), chain structure having 1 to 18 carbon atoms And phosphorus (meth)acrylate alkyl esters.

Moreover, as an acrylic monomer which does not have the said functional group, For example, alkoxyalkyl groups, such as (meth)acrylic acid methoxymethyl, (meth)acrylic acid methoxyethyl, (meth)acrylic acid ethoxymethyl, and (meth)acrylic acid ethoxyethyl. Containing (meth)acrylic acid ester; (Meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as (meth)acrylate phenyl; Non-crosslinkable (meth)acrylamide and derivatives thereof; And (meth)acrylic acid esters having non-crosslinkable tertiary amino groups such as (meth)acrylic acid N,N-dimethylaminoethyl and (meth)acrylic acid N,N-dimethylaminopropyl.

Only one type may be sufficient as the acrylic monomer which does not have the said functional group which comprises the said acrylic polymer (a11), and may be two or more types, and when it is two or more types, the combination and ratio of these can be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; Vinyl acetate; Styrene and the like.

As for the said non-acrylic monomer which comprises the said acrylic polymer (a11), only 1 type may be sufficient, and 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting it is preferably 0.1 to 50% by mass, 1 It is more preferable that it is-40 mass %, and it is especially preferable that it is 3-30 mass %. When the ratio is in this range, in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12), the content of the energy ray-curable group is the curing of the protective film. The degree can be easily adjusted to a desired range.

As for the said acrylic polymer (a11) which comprises the said acrylic resin (a1-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the composition for forming a protective film (IV-1), the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass relative to the total mass of the composition for forming a protective film (IV-1), and 2 to 30% by mass % Is more preferable, and 3 to 20 mass% is particularly preferable.

・Energy ray curable compound (a12)

The energy ray-curable compound (a12) is a group capable of reacting with a functional group of the acrylic polymer (a11), and preferably has one or two or more selected from the group consisting of isocyanate groups, epoxy groups and carboxy groups, and the groups It is more preferable to have an isocyanate group. The energy ray-curable compound (a12), for example, when having an isocyanate group as the group, readily reacts with this hydroxyl group of the acrylic polymer (a11) having the hydroxyl group as the functional group.

The energy ray-curable compound (a12) preferably has 1 to 5 of the energy ray-curable groups in one molecule, and more preferably 1 to 3 particles.

As the energy ray-curable compound (a12), for example, 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (Bisacryloyloxymethyl) ethyl isocyanate; An acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate; And an acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate.

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

As for the said energy ray curable compound (a12) which comprises the said acrylic resin (a1-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the acrylic resin (a1-1), the content ratio of the energy ray-curable group derived from the energy ray-curable compound (a12) to 100 mol% of the content of the functional group derived from the acrylic polymer (a11) is 20. It is preferable that it is -120 mol%, it is more preferable that it is 35-100 mol%, and it is particularly preferable that it is 50-100 mol%. When the content ratio is within this range, the adhesive force of the protective film formed by curing becomes larger. On the other hand, when the energy ray-curable compound (a12) is a monofunctional (having one of the above groups in one molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is In the case of a functional (having two or more of the above groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000 to 2000000, more preferably 300000 to 150,000.

When the polymer (a1) is at least partially crosslinked by a crosslinking agent (f), the polymer (a1) does not correspond to any of the monomers described above, which are described as constituting the acrylic polymer (a11). In addition, the monomer having a group that reacts with the crosslinking agent (f) polymerizes, and may be a crosslinked group in the group that reacts with the crosslinking agent (f), and may be derived from the energy ray-curable compound (a12) to a group that reacts with the functional group. Therefore, it may be crosslinked.

The composition (IV-1) for forming a protective film and the polymer (a1) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80000)

Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80000 include groups containing an energy ray-curable double bond, and preferred examples include (meth)acryloyl groups and vinyl groups. And the like.

The compound (a2) satisfies the above conditions, and the molecular weight is smaller than that of the polymer (a1), but is not particularly limited. And phenol resins.

Among the compound (a2), examples of the low molecular weight compound having an energy ray-curable group include a polyfunctional monomer or oligomer, and an acrylate-based compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylated bisphenol A di(meth) Acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxy Diethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy )Phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (also called tricyclodecanedimethyloldi(meth)acrylate), 1,10-decanedioldi(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, Polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-(( Meta)acryloxyethoxy)phenyl]propane, neopentyl glycoldi(meth)acrylate, ethoxylated polypropylene glycoldi(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, etc. Bifunctional (meth)acrylate;

Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tree (Meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, ethoxylated pentaerythritoltetra(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol Polyfunctional (meth)acrylates such as poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

And polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers.

Among the compounds (a2), epoxy resins having an energy ray-curable group and phenolic resins having an energy ray-curable group can be used, for example, those described in paragraph 0043 of JP 2013-194102 A. These resins also correspond to the resins constituting the thermosetting component (h) described later, but are treated as the compound (a2) in the present invention.

The absolute molecular weight or the weight average molecular weight of the compound (a2) is preferably 100 to 30000, and more preferably 300 to 10000.

The composition (IV-1) for forming a protective film and the compound (a2) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

[Polymer (b) having no energy ray-curable groups]

When the composition for forming a protective film (IV-1) and the film for forming a protective film contain the compound (a2) as the energy ray-curable component (a), it is also necessary to further contain a polymer (b) having no energy ray-curable group. desirable.

The polymer (b) may be at least partially crosslinked with a crosslinking agent (f) described later, or may be uncrosslinked.

Examples of the polymer (b) that does not have an energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethane resins. And the like.

Among these, it is preferable that the said polymer (b) is an acryl-type polymer (it may abbreviate as "acrylic-type polymer (b-1) hereafter.").

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include (meth)acrylic acid alkyl ester, (meth)acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid ester, and hydroxyl group ( And meta)acrylic acid esters and substituted amino group-containing (meth)acrylic acid esters. Here, the "substituted amino group" is as described above.

Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth) )Isobutyl acrylate, (meth)acrylic acid sec-butyl, (meth)acrylic acid tert-butyl, (meth)pentyl acrylate, (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid 2-ethylhexyl, (meth) )Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (( (Meta) acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl (also called (meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)) Alkyl groups constituting alkyl esters such as palmityl acrylate), (meth)acrylic acid heptadecyl and (meth)acrylic acid octadecyl (also called (meth)acrylic acid stearyl), have a chain structure having 1 to 18 carbon atoms. And phosphorus (meth)acrylic acid alkyl esters.

Examples of the (meth)acrylic acid ester having the cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as (meth)acrylic acid isobornyl and (meth)acrylic acid dicyclopentanyl;

(Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;

(Meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;

And (meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester.

As said glycidyl group containing (meth)acrylic acid ester, (meth)acrylic acid glycidyl etc. are mentioned, for example.

Examples of the hydroxyl group-containing (meth)acrylic acid ester include (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxy And propyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

As said substituted amino group containing (meth)acrylic acid ester, (meth)acrylic acid N-methylaminoethyl etc. are mentioned, for example.

Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; Vinyl acetate; And styrene.

As the polymer (b) having at least a part of the energy ray-curable group crosslinked by a crosslinking agent (f), for example, a reactive functional group in the polymer (b) is reacted with a crosslinking agent (f).

The reactive functional group may be appropriately selected depending on the type of the crosslinking agent (f) or the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. Moreover, when a crosslinking agent (f) is an epoxy type compound, a carboxy group, an amino group, an amide group, etc. are mentioned as said reactive functional group, Among these, the carboxy group with high reactivity with an epoxy group is preferable. However, it is preferable that the reactive functional group is a group other than a carboxy group from the viewpoint of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.

As a polymer (b) which has the said reactive functional group and does not have an energy ray curable group, what was obtained by superposing|polymerizing the monomer which has the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer may be used as monomers constituting the monomer. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include, for example, those obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester, and in addition, in the aforementioned acrylic monomer or non-acrylic monomer, one or What is obtained by superposing|polymerizing the monomer which 2 or more hydrogen atoms are substituted by the said reactive functional group is mentioned.

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

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably from 10000 to 2000000, and from 100000 to 150,000, from the viewpoint that the film forming property of the protective film-forming composition (IV-1) is better. It is more preferable.

The composition (IV-1) for forming a protective film and the polymer (b) having no energy ray-curable group contained in the film for forming a protective film may be one type, two or more types, or combinations and ratios of two or more types Can be arbitrarily selected.

As the composition (IV-1) for forming a protective film, there may be mentioned those containing either or both of the polymer (a1) and the compound (a2) in addition to the compound (p). In addition, when the composition (IV-1) for forming a protective film contains the compound (a2), it is preferable to further contain a polymer (b) that does not have an energy ray-curable group, and in this case, the above (a1) It is also preferable to contain. Moreover, the composition (IV-1) for forming a protective film may not contain the compound (a2), and may also contain the polymer (a1) and a polymer (b) having no energy ray-curable groups.

When the composition (IV-1) for forming a protective film contains the polymer (a1), the compound (a2), and a polymer (b) having no energy ray-curable group, in the composition for forming a protective film (IV-1), the The content of the compound (a2) is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass, relative to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) that does not have an energy ray-curable group. .

In the composition for forming a protective film (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (i.e., the formation of a protective film) The total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the film for forming a protective film relative to the total mass of the molten film) is preferably 5 to 90% by mass, and 10 to 80 It is more preferable that it is a mass %, and it is especially preferable that it is 15-70 mass %, For example, any one of 20-60 mass% and 25-50 mass% may be sufficient. When the said total content ratio is such a range, energy ray curability of a film for protective film formation becomes more favorable.

When the composition (IV-1) for forming a protective film contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, in the composition for forming a protective film (IV-1) and the film for forming a protective film , The content of the polymer (b) is preferably 50 to 400 parts by mass, more preferably 100 to 350 parts by mass, particularly 150 to 300 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable component (a) desirable. When the content of the polymer (b) is within this range, the energy ray curability of the film for forming a protective film becomes better.

Depending on the purpose, the composition for forming a protective film (IV-1) is a photopolymerization initiator (c), a filler (d) other than the energy ray-curable component (a), a polymer (b) having no energy ray-curable group, and a compound (p). , Coupling agent (e), crosslinking agent (f), colorant (g), thermosetting component (h), curing accelerator (i) and one or more selected from the group consisting of general-purpose additives (z) do.

For example, by using the composition for forming a protective film (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the film for forming a protective film formed has an adhesive force to an adherend by heating. The strength of the protective film formed from the film for forming a protective film is also improved.

[Photopolymerization initiator (c)]

As the photopolymerization initiator (c), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoate and methyl benzoin dimethyl ketal, etc. Benzoin compounds; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; Α-ketol compounds such as 1-hydroxycyclohexylphenylketone; Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; Benzophenone and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H Benzophenone compounds such as -carbazol3-yl]-,1-(O-acetyloxime); Peroxide compounds; Diketone compounds such as diacetyl; benzyl; Dibenzyl; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone and; 2-chloroanthraquinone, etc. are mentioned.

Moreover, as a photoinitiator (c), For example, quinone compounds, such as 1-chloro anthraquinone; And photosensitizers such as amines.

As for the photopolymerization initiator (c) contained in the composition for forming a protective film (IV-1), only one type may be used, or two or more types may be used. In the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the photopolymerization initiator (c) is used, in the composition (IV-1) for forming a protective film, the content of the photopolymerization initiator (c) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound (a). It is preferable, it is more preferably 0.03 to 15 parts by mass, and particularly preferably 0.05 to 10 parts by mass.

[Filling material (d)]

When the film for forming a protective film contains a filler (d), the protective film obtained by curing the film for forming a protective film can easily adjust the thermal expansion coefficient. Then, by optimizing the coefficient of thermal expansion for the object to be formed of the protective film, the reliability of the package obtained using the composite sheet for forming the protective film is further improved. In addition, when the film for forming a protective film contains a filler (d), the moisture absorption rate of the protective film can be reduced or heat dissipation can be improved.

As a filler (d), what consists of a heat conductive material is mentioned, for example.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.

Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide and boron nitride; Beads in which these inorganic fillers are spheroidized; Surface modified products of these inorganic fillers; Single crystal fibers of these inorganic fillers; And glass fibers.

Among these, it is preferable that the inorganic filler is silica or alumina.

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

On the other hand, indicates the value of the "average particle diameter" means a particle diameter (D ₅₀₎ of from, integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method in particular there is no mention in the specification .

The composition (IV-1) for forming a protective film and the filler (d) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the filler (d) is used, in the composition (IV-1) for forming a protective film, the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the filler (d) of the film for forming a protective film) The content of) is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, particularly preferably 30 to 75% by mass, for example, 40 to 70% by mass and 45 to 65% by mass % May be any one. When the content of the filler (d) is within this range, adjustment of the thermal expansion coefficient becomes easier.

[Coupling agent (e)]

As the coupling agent (e), by using a functional group capable of reacting with an inorganic compound or an organic compound, adhesion and adhesion to the adherend of the film for forming a protective film can be improved. Moreover, by using the coupling agent (e), the protective film obtained by hardening the film for protective film formation does not impair heat resistance, and water resistance is improved.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray-curable component (a), a polymer (b) having no energy ray-curable group, etc., and more preferably a silane coupling agent.

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycine Cydyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-( 2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltri Ethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

The composition (IV-1) for forming a protective film and the coupling agent (e) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the coupling agent (e) is used, in the composition for forming a protective film (IV-1) and the film for forming a protective film, the content of the coupling agent (e) is a polymer having no energy ray-curable component (a) and an energy ray-curable group It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content of (b), it is more preferable that it is 0.05-10 mass parts, and it is especially preferable that it is 0.1-5 mass parts. When the content of the coupling agent (e) is greater than or equal to the above lower limit, the use of the coupling agent (e), such as improving the dispersibility of the filler (d) with respect to the resin or improving the adhesion of the protective film forming film to the adherend, etc. The effect is obtained more remarkably. Moreover, generation|occurrence|production of outgas is suppressed more because the said content of the coupling agent (e) is below the said upper limit.

[Crosslinking system (f)]

By crosslinking the above-mentioned energy ray-curable component (a) or the polymer (b) having no energy ray-curable group using the crosslinking agent (f), the initial adhesive strength and cohesive strength of the film for forming a protective film can be adjusted.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate-based crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine-based crosslinking agent (a crosslinking agent having an aziridinyl group), and the like.

As said organic polyvalent isocyanate compound, For example, aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound, and alicyclic polyvalent isocyanate compound (Hereinafter, these compounds may be abbreviated as "aromatic polyvalent isocyanate compound, etc."); Trimers, isocyanurates and adducts such as the aromatic polyvalent isocyanate compounds; And terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compound with a polyol compound. The "adduct" is a reactant of the aromatic polyvalent isocyanate compound, aliphatic polyisocyanate compound or alicyclic polyvalent isocyanate compound, and a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Means Examples of the adducts include xylylenediisocyanate adducts of trimethylolpropane as described later. In addition, "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at the terminal end of the molecule.

As said organic polyvalent isocyanate compound, More specifically, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylenediisocyanate; 1,4-xylenediisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; A compound in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to hydroxyl groups of all or part of a polyol such as trimethylolpropane; And lysine diisocyanate.

Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinyl propionate, And tetramethylolmethane-tri-β-aziridinylpropionate and N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylenemelamine.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group. When the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) without an energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray-curable component (a) or the energy ray-curable group By the reaction of the polymer (b) not having, a crosslinked structure can be easily introduced into the film for forming a protective film.

As for the composition (IV-1) for forming a protective film and the crosslinking agent (f) contained in the film for forming a protective film, only 1 type may be sufficient, and 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

When the crosslinking agent (f) is used, in the composition for forming a protective film (IV-1), the content of the crosslinking agent (f) is the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group 100 It is preferable that it is 0.01-20 mass parts with respect to mass part, it is more preferable that it is 0.1-10 mass parts, and it is especially preferable that it is 0.5-5 mass parts. When the said content of crosslinking agent (f) is more than the said lower limit, the effect by using crosslinking agent (f) is obtained more remarkably. Moreover, when the said content of crosslinking agent (f) is below the said upper limit, excessive use of crosslinking agent (f) is suppressed.

[Colorant (g)]

As a coloring agent (g), well-known things, such as an inorganic type pigment, an organic type pigment, and an organic type dye, are mentioned, for example.

Examples of the organic pigments and organic dyes include, for example, aluminum-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squarylium-based dyes, azurenium-based dyes, polymethine-based dyes, and naphthoquinone-based dyes. , Pyryllium pigment, phthalocyanine pigment, naphthalocyanine pigment, naphtholactam pigment, azo pigment, condensed azo pigment, indigo pigment, perinone pigment, perylene pigment, dioxazine pigment, quinacridone pigment, Isoindolinone pigment, quinophthalone pigment, pyrrole pigment, thioindigo pigment, metal complex pigment (metal complex dye), dithiol metal complex pigment, indolphenol pigment, triarylmethane pigment, anthra And quinone-based dyes, naphthol-based dyes, azomethine-based dyes, benzimidazole-based dyes, pyrantrone-based dyes, and styrene-based dyes.

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

The composition (IV-1) for forming a protective film and the colorant (g) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the coloring agent (g) is used, the content of the protective film forming composition (IV-1) and the coloring agent (g) of the protective film forming film may be appropriately adjusted according to the purpose. For example, by controlling the content of the colorant (g) and controlling the light transmittance of the protective film to control the printing visibility, in the composition for forming a protective film (IV-1), the total content of all components other than the solvent The content ratio of the colorant (g) to (ie, the content of the colorant (g) of the film for forming a protective film) is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and 0.8 to 5% by mass It is particularly preferred to be. When the said content of the coloring agent (g) is more than the said lower limit, the effect by using a coloring agent (g) is obtained more remarkably. Moreover, excessive use of the coloring agent (g) is suppressed by the said content of the coloring agent (g) being below the said upper limit.

[Thermosetting component (h)]

The composition (IV-1) for forming a protective film and the thermosetting component (h) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

Examples of the thermosetting component (h) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy-based thermosetting resins are preferred.

(Epoxy watch thermosetting resin)

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

The composition for forming a protective film (IV-1) and the epoxy-based thermosetting resin contained in the film for forming a protective film may be one type, or two or more types, and when two or more types, combinations and ratios thereof may be arbitrarily selected.

·Epoxy resin (h1)

As an epoxy resin (h1), a well-known thing is mentioned, For example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its additive, orthocresol novolak epoxy resin, dicyclopenta And bifunctional or higher epoxy compounds such as diene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins.

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

As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by converting a part of the epoxy group of a polyfunctional epoxy resin into a group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained, for example, by adding (meth)acrylic acid or a derivative thereof to an epoxy group.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple|bonded with the aromatic ring which comprises an epoxy resin etc. are mentioned, for example.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also called a vinyl group), a 2-propenyl group (also called an allyl group), a (meth)acryloyl group, and a (meth)acrylamide group. And an acryloyl group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but from the viewpoint of the curability of the film for forming a protective film and the strength and heat resistance of the protective film, it is preferably 300 to 30000, more preferably 400 to 10000, 500 It is especially preferable to be 3,000.

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

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

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

Epoxy resin (h1) may be used alone or in combination of two or more, and when two or more are used in combination, the combination and proportion thereof may be arbitrarily selected.

·Heat curing agent (h2)

The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).

The thermosetting agent (h2) includes, for example, 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 and a group in which an acid group is anhydride, and a phenolic hydroxyl group, an amino group, or an acid group in anhydride is preferred, and is preferably phenolic. It is more preferable that it is a hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins. Can.

Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include, for example, a compound formed by partially replacing a hydroxyl group of a phenol resin with a group having an unsaturated hydrocarbon group, and a compound formed by directly bonding a group having an unsaturated hydrocarbon group to the aromatic ring of the phenol resin. Can be lifted.

The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the aforementioned unsaturated hydrocarbon group.

When a phenolic curing agent is used as the heat curing agent (h2), it is preferable that the heat curing agent (h2) has a high softening point or a glass transition temperature, since the peelability from the support sheet of the protective film is improved.

In the present specification, the “glass transition temperature” refers to a DSC curve of a sample using a differential scanning calorimeter, and is represented by the temperature of the inflection point of the obtained DSC curve.

Among the thermosetting agents (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene-based phenol resin, and aralkylphenol resin is preferably 300 to 30000 , It is more preferably 400 to 10000, and particularly preferably 500 to 3000.

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

As the thermosetting agent (h2), one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof may be arbitrarily selected.

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

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

[Hardening accelerator (i)]

The curing accelerator (i) is a component for adjusting the curing rate of the film for forming a protective film.

Preferred curing accelerators (i) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethyl imidazole; Organic phosphine such as tributylphosphine, diphenylphosphine and triphenylphosphine; And tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate.

The curing accelerator (i) may be used alone, or two or more may be used in combination, and when two or more are used in combination, the combination and proportion thereof may be arbitrarily selected.

In the case of using the curing accelerator (i), the content of the curing accelerator (i) of the protective film forming composition (IV-1) and the protective film forming film is not particularly limited, and may be appropriately selected depending on the components used in combination.

[Universal additive (z)]

The general-purpose additive (z) may be a known one, and may be arbitrarily selected according to the purpose, and is not particularly limited, and examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a gettering agent.

The composition (IV-1) for forming a protective film and the general-purpose additive (z) contained in the film for forming a protective film may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

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

[menstruum]

It is preferable that the composition for forming a protective film (IV-1) further contains a solvent. The composition (IV-1) for forming a protective film containing a solvent has good handleability.

The solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; And amides (compounds having amide bonds) such as dimethylformamide and N-methylpyrrolidone.

The solvent contained in the protective film-forming composition (IV-1) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

The solvent contained in the protective film-forming composition (IV-1) is preferably methyl ethyl ketone, toluene, ethyl acetate, or the like, because the components contained in the protective film-forming composition (IV-1) can be more uniformly mixed.

<<The manufacturing method of a composition for forming a protective film>>

The composition for forming a protective film, such as the composition for forming a protective film (IV-1), is obtained by blending each component for constituting it.

The order of addition when mixing each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, the solvent may be mixed with any other blending component other than the solvent to dilute the blending component in advance, or may be used without diluting any blending component other than the solvent in advance. You may use it by mixing with these compounding components.

The method of mixing each component when blending is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade or the like; A method of mixing using a mixer; You may select suitably from well-known methods, such as the method of adding and mixing ultrasonic waves.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Method of manufacturing a film for forming a protective film

The film for forming a protective film can be prepared by coating a composition for forming a protective film on a release film (preferably, its peeling treatment surface) and drying it as necessary. The manufacturing method at this time is as described above.

On the other hand, the film for forming a protective film is, for example, as shown in Fig. 1, usually stored in a state where a release film is pasted on both sides. To this end, if a peeling film (preferably, the peeling treatment surface) is added to the exposed surface of the film for forming a protective film (the side opposite to the side having the peeling film) formed on the peeling film as described above, do.

◇How to use the film for forming a protective film

As described above, the film for forming a protective film can be formed on a supporting sheet to form a composite sheet for forming a protective film. The composite sheet for forming a protective film is affixed to the back surface of the semiconductor wafer (a surface opposite to the electrode forming surface) by the film for forming a protective film. Then, from this state, a target semiconductor chip and a semiconductor device can be manufactured by a manufacturing method described later.

On the other hand, the film for forming a protective film may be first formed on the back surface of the semiconductor wafer, not the support sheet. For example, first, a film for forming a protective film is affixed to the back surface of a semiconductor wafer, and a support sheet is affixed to the exposed surface of the film for forming a protective film (a side opposite to the side affixed to the semiconductor wafer), or this affix After the energy ray is irradiated to the film for forming a protective film in one state, cured to form a protective film, a supporting sheet is bonded to the exposed surface of the protective film (the side opposite to the side affixed to the semiconductor wafer) to form a protective film composite Sheet. Then, from this state, a target semiconductor chip and a semiconductor device can be manufactured by a manufacturing method described later.

◇Composite sheet for protective film formation

The composite sheet for forming a protective film according to one embodiment of the present invention includes a support sheet, and is provided with the film for forming a protective film on the support sheet.

In the present invention, even after the film for forming a protective film is cured, as long as the laminated structure of the cured product of the support sheet and the film for forming a protective film (in other words, the support sheet and the protective film) is maintained, this laminated structure is formed as "protective film formation. Dragon Composite Sheet”.

The thickness of the semiconductor wafer to be used for the composite sheet for forming a protective film of the present invention is not particularly limited, but is preferably 30 to 1000 µm, and 100 to 400 µm, in terms of easier division into semiconductor chips described later. It is more preferable.

Hereinafter, the structure of the composite sheet for forming a protective film will be described in detail.

◎ Support sheet

The support sheet may be composed of one layer (single layer), or may be composed of two or more layers. When a support sheet consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited, unless the effect of this invention is impaired.

Preferred support sheets include, for example, provided with a substrate, and the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate (the base material and the pressure-sensitive adhesive layer are directly contacted and laminated in this order); A base material, an intermediate layer and a pressure-sensitive adhesive layer are laminated in this order in direct contact in their thickness direction; And things consisting of only a substrate.

Examples of the composite sheet for forming a protective film of the present invention will be described below with reference to the drawings for each type of the support sheet.

2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.

On the other hand, in the drawings after FIG. 2, the same components as those shown in the already described drawings are given the same reference numerals as in the case of the described drawings, and detailed description thereof is omitted.

The composite sheet 1A for forming a protective film shown here is provided with a base 11, an adhesive layer 12 on the base 11, and a film 13 for forming a protective film on the adhesive layer 12. I have it. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1A for forming a protective film is, in other words, one surface of the support sheet 10 (in this specification, the "first" It may be referred to as &quot;plane&quot;), and has a configuration in which the film 13 for forming a protective film is laminated on 10a. In addition, the composite sheet 1A for forming a protective film is further provided with a release film 15 on the film 13 for forming a protective film.

In the composite sheet for forming a protective film 1A, the pressure-sensitive adhesive layer 12 is laminated on one surface of the substrate 11 (sometimes referred to as "first surface" in this specification) 11a, and the pressure-sensitive adhesive layer A film 13 for forming a protective film is laminated on the entire surface of one surface of (12) (which may be referred to as a "first surface" in this specification) 12a, and the first film of the film 13 for forming a protective film. A part of the surface 13a, that is, the adhesive layer 16 for a jig is laminated on an area near the periphery, and the adhesive layer 16 for a jig is laminated on the first surface 13a of the film 13 for forming a protective film The release film 15 is laminated on the surface which is not present and on the surface 16a (top and side surfaces) of the adhesive layer for jig 16.

In the composite sheet 1A for forming a protective film, the film 13 for forming a protective film is energy ray curable, and satisfies the above-mentioned conditions of adhesive strength and shear strength.

The jig adhesive layer 16 may be, for example, of a single-layer structure containing an adhesive component, or of a multi-layer structure in which a layer containing an adhesive component is laminated on both sides of a sheet serving as a core material.

In the composite sheet 1A for forming a protective film shown in FIG. 2, the release film 15 is removed, and the back surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film. In addition, an upper surface of the surface 16a of the adhesive layer for jig 16 is attached to a jig such as a ring frame and used.

3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.

The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 2 except that the adhesive layer 16 for a jig is not provided. That is, in the composite sheet 1B for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film is formed on the front surface of the first surface 12a of the pressure-sensitive adhesive layer 12. The forming film 13 is laminated, and the release film 15 is laminated on the entire surface of the first surface 13a of the protective film forming film 13.

In the composite sheet 1B for forming a protective film, the film 13 for forming a protective film is energy ray curable, and satisfies the above-mentioned conditions of adhesive strength and shear strength.

The composite sheet 1B for forming a protective film shown in FIG. 3 is in a state where the release film 15 is removed, and a semiconductor wafer (not shown) is provided in a central portion of the first surface 13a of the film 13 for forming a protective film. ) Is affixed to the back surface, and in addition, an area near the periphery is affixed to a jig such as a ring frame and used.

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

The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 2 except that the pressure-sensitive adhesive layer 12 is not provided. That is, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed of only the base 11. Then, the film 13 for forming a protective film is laminated on the first surface 11a (the first surface 10a of the support sheet 10) of the substrate 11, and the first surface of the film 13 for forming a protective film A part of (13a), that is, the adhesive layer for jig 16 is laminated in a region near the periphery, and the adhesive layer for jig 16 is not laminated on the first surface 13a of the film 13 for forming a protective film The release film 15 is laminated on the unexposed area and the surface 16a (top and side surfaces) of the jig adhesive layer 16.

In the composite sheet 1C for forming a protective film, the film 13 for forming a protective film is energy ray-curable, and satisfies the above-mentioned conditions of adhesive strength and shear strength.

The composite sheet 1C for forming a protective film shown in FIG. 4 is the same as the composite sheet 1A for forming a protective film shown in FIG. 2, with the release film 15 removed, the first of the film 13 for forming a protective film The back surface of the semiconductor wafer (not shown) is affixed to the surface 13a, and in addition, an upper surface of the surface 16a of the adhesive layer 16 for the jig is affixed to a jig such as a ring frame.

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

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in FIG. 4 except that the adhesive layer 16 for a jig is not provided. That is, in the composite sheet 1D for forming a protective film, the film 13 for forming a protective film is laminated on the first surface 11a of the substrate 11, and the first surface 13a of the film 13 for forming a protective film A release film 15 is laminated on the entire surface of the.

In the composite sheet 1D for forming a protective film, the film 13 for forming a protective film is energy ray curable, and satisfies the above-described conditions of adhesive strength and shear strength.

The composite sheet 1D for forming a protective film shown in FIG. 5 is the same as the composite sheet 1B for forming a protective film shown in FIG. 3, with the release film 15 removed, and the first of the protective film forming film 13 Among the surfaces 13a, a back surface of a semiconductor wafer (not shown) is affixed to a portion of the central side, and in addition, a region near the periphery is affixed to a jig such as a ring frame.

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

The composite sheet for forming a protective film 1E shown here is the same as the composite sheet for forming a protective film 1B shown in FIG. 3 except that the shape of the film for forming a protective film is different. That is, the composite sheet 1E for forming a protective film is provided with a substrate 11, an adhesive layer 12 is provided on the substrate 11, and a protective film forming film 23 is provided on the adhesive layer 12. Is done by The support sheet 10 is a laminate of the substrate 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1E for forming a protective film is, in other words, for forming a protective film on the first surface 10a of the support sheet 10 The film 23 has a stacked configuration. In addition, the composite sheet 1E for forming a protective film is further provided with a release film 15 on the film 23 for forming a protective film.

In the composite sheet 1E for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and a part of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the center A protective film forming film 23 is laminated on the side region. Then, the first layer 12a of the pressure-sensitive adhesive layer 12 is peeled on the surface 23a (top and side surfaces) of the film 23 for forming a protective film and the area where the film 23 for forming a protective film is not laminated. The film 15 is laminated.

When the composite sheet 1E for forming a protective film is viewed in a plan view from above, the film 23 for forming a protective film has a smaller surface area than the pressure-sensitive adhesive layer 12 and has a shape such as, for example, a circular shape.

In the composite sheet 1E for forming a protective film, the film 23 for forming a protective film is energy ray curable, and satisfies the above-mentioned conditions of adhesive strength and shear strength.

In the composite sheet 1E for forming a protective film shown in FIG. 6, the release film 15 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the surface 23a of the film 23 for forming a protective film, and is added In the first surface 12a of the pressure-sensitive adhesive layer 12, a region in which the film 23 for forming a protective film is not laminated is attached to a jig such as a ring frame and used.

On the other hand, in the composite sheet 1E for forming a protective film shown in Fig. 6, in the area where the film 23 for forming a protective film is not laminated, on the first surface 12a of the pressure-sensitive adhesive layer 12, Figs. The adhesive layer for jig may be laminated|stacked similarly to what is shown in (not shown). The composite sheet 1E for forming a protective film provided with the adhesive layer for a jig is used in the same manner as the composite sheet for forming a protective film shown in FIGS. 2 and 4 with the surface of the adhesive layer for a jig attached to a jig such as a ring frame. .

In this way, the composite sheet for forming a protective film may be provided with an adhesive layer for a jig even if the support sheet and the film for forming a protective film are in any form. However, as shown in Figs. 2 and 4, as a composite sheet for forming a protective film provided with an adhesive layer for jigs, it is preferable to provide an adhesive layer for jigs on a film for forming a protective film.

The composite sheet for forming a protective film according to one embodiment of the present invention is not limited to those shown in Figs. 2 to 6, and some configurations of those shown in Figs. 2 to 6 are changed within a range that does not impair the effects of the present invention. Alternatively, it may be deleted, or another configuration may be added to the ones described so far.

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

In addition, in the composite sheet for forming a protective film shown in FIGS. 2, 3 and 6, an intermediate layer may be formed between the base 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by laminating a base material, an intermediate layer, and an adhesive layer in this order in these thickness directions. Here, the intermediate layer is the same as the intermediate layer which may be formed in the composite sheet for forming a protective film shown in FIGS. 4 and 5.

In addition, in the composite sheet for forming a protective film shown in FIGS. 2 to 6, layers other than the intermediate layer may be formed at any point.

In addition, in the composite sheet for forming a protective film, some gaps may be formed between the release film and the layer in direct contact with the release film.

In addition, in the composite sheet for forming a protective film, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, as will be described later, it is preferable that a layer in direct contact with the film for forming a protective film of the support sheet, such as an adhesive layer, is non-energy ray curable. Such a composite sheet for forming a protective film enables easier pickup of a semiconductor chip on which the protective film is formed.

The support sheet may be transparent, opaque, or colored depending on the purpose.

Especially, in this invention in which the film for protective film formation has energy ray curability, it is preferable that a support sheet transmits energy rays.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in this range, when the film for forming a protective film is irradiated with energy rays (ultraviolet rays) through a support sheet, the degree of curing of the film for forming a protective film is further improved.

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

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

When the transmittance of the light is in this range, when the film for protective film formation or the protective film is irradiated with laser light through the support sheet and printed thereon, printing can be performed more clearly.

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

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

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

Moreover, in the support sheet, the transmittance of light having a wavelength of 1342 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in this range, the semiconductor wafer may be irradiated with laser light through a support sheet and a film or protective film for forming a protective film, and the modified layer may be more easily formed on the semiconductor wafer.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1342 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

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

○ List

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

Examples of the resin include polyethylene such as low density polyethylene (LDPE), straight chain low density polyethylene (LLDPE), and high density polyethylene (HDPE); Polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer (copolymer obtained by using ethylene as a monomer) ; Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resin obtained using vinyl chloride as a monomer); polystyrene; Polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and all aromatic polyesters in which all constituent units have aromatic cyclic groups; Copolymers of two or more of the above polyesters; Poly(meth)acrylic acid esters; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone; And polyether ketones.

Further, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. It is preferable that the polymer alloy of the above-mentioned polyester and other resins has a relatively small amount of resin other than polyester.

Moreover, as said resin, For example, the 1 or 2 or more types of the crosslinked resin which the above-mentioned resin demonstrated above were bridge|crosslinked; And modified resins such as ionomers using one or two or more of the resins exemplified so far.

The resin constituting the base material may be one kind, or two or more kinds, and in the case of two or more kinds, combinations and ratios thereof may be arbitrarily selected.

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

The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 100 μm. When the thickness of the substrate is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or semiconductor chip are further improved.

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

It is preferable that the substrate has high precision in thickness, that is, variation in thickness is suppressed regardless of the portion. Among the above-mentioned constituent materials, materials that can be used for constructing a substrate having high precision of such thickness include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers.

The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the resin.

It is preferable that the optical properties of the substrate satisfy the optical properties of the support sheet described above. For example, the substrate may be transparent, opaque, colored depending on the purpose, or another layer may be deposited.

In addition, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the substrate transmits energy rays.

In order to improve the adhesion with other layers such as a pressure-sensitive adhesive layer formed thereon, the substrate is subjected to an uneven treatment by sand blasting, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, Oxidation treatments, such as flame treatment, chromic acid treatment, and hot air treatment, may be applied to the surface.

Moreover, the surface of the base material may have been subjected to a primer treatment.

In addition, the base material is an antistatic coat layer; When the composite sheet for forming a protective film is superimposed and stored, the substrate may adhere to another sheet, or may have a layer or the like that prevents the substrate from adhering to the adsorption table.

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 resin.

○Adhesive layer

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

Examples of the pressure-sensitive adhesive include acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, epoxy-based resins, adhesive resins such as polyvinyl ether and polycarbonate, and ester-based resins, and acrylic resins are preferred.

On the other hand, in the present invention, "adhesive resin" is a concept including both a resin having an adhesive property and a resin having an adhesive property. For example, not only the resin itself has adhesive properties, but also other components such as additives It also includes resins exhibiting tackiness by using together, resins exhibiting tackiness due to the presence of a trigger such as heat or water.

The pressure-sensitive adhesive layer may be composed of one layer (single layer), or may be composed of a plurality of layers of two or more layers, and in the case of a plurality of layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is particularly limited. Does not work.

The thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.

Here, the "thickness of the adhesive layer" means the entire thickness of the pressure-sensitive adhesive layer, and, for example, the thickness of the pressure-sensitive adhesive layer composed of multiple layers means the total thickness of all the layers constituting the pressure-sensitive adhesive layer.

It is preferable that the optical properties of the pressure-sensitive adhesive layer satisfy the optical properties of the support sheet described above. For example, the pressure-sensitive adhesive layer may be transparent or opaque, and may be colored depending on the purpose.

Further, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the pressure-sensitive adhesive layer transmits energy rays.

The pressure-sensitive adhesive layer may be formed using an energy ray curable pressure sensitive adhesive, or may be formed using a non-energy ray curable pressure sensitive adhesive. The pressure-sensitive adhesive layer formed by using an energy ray-curable pressure-sensitive adhesive can easily control physical properties before and after curing.

<<adhesive composition>>

The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target site by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying it as necessary. A more specific method of forming the pressure-sensitive adhesive layer will be described in detail later along with the method of forming another layer. In the pressure-sensitive adhesive composition, the content ratio of components that are not vaporized at room temperature is usually the same as the content ratio of the components in the pressure-sensitive adhesive layer.

Coating of the pressure-sensitive adhesive composition may be carried out by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, myer bar And a method of using various coaters such as a coater and a kiss coater.

The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferable to heat-dry. It is preferable to dry the pressure-sensitive adhesive composition containing a solvent, for example, at 70 to 130° C. for 10 seconds to 5 minutes.

When the pressure-sensitive adhesive layer is an energy ray-curable pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive, that is, as the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray curable pressure-sensitive adhesive resin (I-1a) (hereinafter, ``adhesive resin ( I-1a)” and the pressure-sensitive adhesive composition (I-1) containing an energy ray-curable compound; Contains the energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)"). Pressure-sensitive adhesive composition (I-2); And an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.

<Adhesive composition (I-1)>

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

[Adhesive resin (I-1a)]

It is preferable that the said adhesive resin (I-1a) is an acrylic resin.

As said acryl-type resin, the acryl-type polymer which has a structural unit derived from (meth)acrylic-acid alkylester at least is mentioned, for example.

As for the structural unit which the said acrylic resin has, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

Examples of the (meth)acrylic acid alkyl ester include those having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the alkyl group is preferably linear or branched.

As the (meth)acrylic acid alkyl ester, more specifically, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)isopropyl acrylate, (meth)n-butyl acrylate, (meth) )Isobutyl acrylate, (meth)acrylic acid sec-butyl, (meth)acrylic acid tert-butyl, (meth)pentyl acrylate, (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid 2-ethylhexyl, (meth) )Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (( (Meta) acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl (also called (meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)) And also called palmityl acrylate), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl (also called (meth)acrylic acid stearyl), (meth)acrylic acid nonadecyl, and (meth)acrylic acid icosyl.

From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, it is preferable that the acrylic polymer has a structural unit derived from (meth)acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group. In addition, from the viewpoint of further improving the adhesive strength of the pressure-sensitive adhesive layer, the carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8. In addition, it is preferable that the (meth)acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is a methacrylic acid alkyl ester.

It is preferable that the said acrylic polymer has a structural unit derived from a functional group containing monomer in addition to the structural unit derived from (meth)acrylic acid alkylester.

As the functional group-containing monomer, for example, introduction of an unsaturated group into the side chain of an acrylic polymer by, for example, the functional group reacting with a crosslinking agent described below to become a starting point for crosslinking or reacting with an unsaturated group in an unsaturated group-containing compound described below. And what makes it possible.

Among the functional group-containing monomers, examples of the functional group include hydroxyl groups, carboxyl groups, amino groups, and epoxy groups.

That is, examples of the functional group-containing monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers.

Examples of the hydroxyl group-containing monomer include (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, and (meth) (Meth)acrylic acid hydroxyalkyl, such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; And non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols having no (meth)acryloyl skeleton).

Examples of the carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid (monocarboxylic acids having ethylenically unsaturated bonds); Ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid (dicarboxylic acids having ethylenically unsaturated bonds); Anhydride of the ethylenically unsaturated dicarboxylic acid; And (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

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

As for the functional group containing monomer which comprises the said acrylic polymer, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass, and more preferably 3 to 30% by mass, relative to the total amount of the structural units. It is particularly preferred to be.

The said acrylic polymer may have a structural unit derived from another monomer other than the structural unit derived from the (meth)acrylic-acid alkylester and the functional group-containing monomer.

The other monomer is not particularly limited as long as it is copolymerizable with (meth)acrylic acid alkyl ester and the like.

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

As for the said other monomer which comprises the said acrylic polymer, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

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

On the other hand, the reaction of the functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the above-mentioned energy ray curable adhesive resin (I-2a).

As for the adhesive resin (I-1a) contained in the adhesive composition (I-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive resin (I-1a) relative to the total content of components other than the solvent is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, It is particularly preferably 15 to 90% by mass.

[Energy ray curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include a monomer or oligomer that has an energy ray-polymerizable unsaturated group and is curable by irradiation with energy rays.

Among the energy ray-curable compounds, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Polyvalent (meth)acrylates such as 1,4-butylene glycol di(meth)acrylate and 1,6-hexanediol (meth)acrylate; Urethane (meth)acrylate; Polyester (meth)acrylate; Polyether (meth)acrylate; And epoxy (meth)acrylates.

Among the energy ray-curable compounds, for example, oligomers formed by polymerizing the monomers exemplified above are mentioned as oligomers.

Urethane (meth)acrylates and urethane (meth)acrylate oligomers are preferred because the energy ray-curable compound has a relatively high molecular weight and is difficult to lower the storage elastic modulus of the pressure-sensitive adhesive layer.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass, based on the total content of components other than the solvent of the pressure-sensitive adhesive composition (I-1), and 5 to It is more preferable that it is 90 mass %, and it is especially preferable that it is 10 to 85 mass %.

[Crosslinking system]

When using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkyl ester as the adhesive resin (I-1a), the adhesive composition (I-1) is additionally It is preferable to contain a crosslinking agent.

The crosslinking agent, for example, reacts with the functional group to crosslink adhesive resins (I-1a).

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy-based crosslinking agents such as ethylene glycol glycidyl ether (crosslinking agents having a glycidyl group); Aziridine-based crosslinking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphatrizine (crosslinking agent having an aziridinyl group); Metal chelate-based crosslinking agents such as aluminum chelate (crosslinking agents having a metal chelate structure); And isocyanurate-based crosslinking agents (crosslinking agents having an isocyanuric acid skeleton).

It is preferable that the crosslinking agent is an isocyanate-based crosslinking agent from the viewpoint of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesion of the pressure-sensitive adhesive layer and ease of availability.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 100 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferable that it is -15 parts by mass.

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Phosphorus compounds; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; Α-ketol compounds such as 1-hydroxycyclohexylphenylketone; Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; Peroxide compounds; Diketone compounds such as diacetyl; benzyl; Dibenzyl; Benzophenone; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; And 2-chloroanthraquinone.

Moreover, as said photoinitiator, For example, quinone compounds, such as 1-chloro anthraquinone; It is also possible to use photosensitizers such as amines.

As for the photoinitiator contained in the adhesive composition (I-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable compound. It is particularly preferable that it is a mass part.

[Other additives]

The pressure-sensitive adhesive composition (I-1) may contain other additives that do not correspond to any of the above-described components within a range that does not impair the effects of the present invention.

Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction retarders and crosslinking accelerators (catalysts) ) And well-known additives.

On the other hand, the reaction retardant means that, for example, an undesired crosslinking reaction proceeds in the pressure-sensitive adhesive composition (I-1) under the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It is to suppress. Examples of the reaction retarding agent include forming a chelate complex by chelation with respect to the catalyst, and more specifically, those having two or more carbonyl groups (-C(=O)-) in one molecule are mentioned. have.

As for the other additives contained in the pressure-sensitive adhesive composition (I-1), only one type may be used, or two or more types thereof may be used, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

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

[menstruum]

The pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, coating suitability to a coating target surface is improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; Esters such as ethyl acetate (carboxylic acid ester); Ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as cyclohexane and n-hexane; Aromatic hydrocarbons such as toluene and xylene; And alcohols such as 1-propanol and 2-propanol.

As the above-mentioned solvent, for example, the one used in the production of the adhesive resin (I-1a) may not be removed from the adhesive resin (I-1a), and may be used in the adhesive composition (I-1) as it is, and the adhesive resin (I A solvent of the same or different type as that used in the preparation of -1a) may be added separately in the preparation of the pressure-sensitive adhesive composition (I-1).

As for the solvent contained in the adhesive composition (I-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

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

<Adhesive composition (I-2)>

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

[Adhesive resin (I-2a)]

The said adhesive resin (I-2a) is obtained by making the functional group in the adhesive resin (I-1a) react with the unsaturated group containing compound which has an energy ray polymerizable unsaturated group, for example.

The unsaturated group-containing compound is a compound having a group capable of bonding with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.

Examples of the energy ray polymerizable unsaturated group include (meth)acryloyl group, vinyl group (also referred to as ethenyl group) and allyl group (also referred to as 2-propenyl group), and (meth)acryloyl group. Is preferred.

Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group.

Examples of the unsaturated group-containing compound include (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, and glycidyl (meth)acrylate.

As for the adhesive resin (I-2a) contained in the adhesive composition (I-2), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) with respect to the total mass of components other than the solvent is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, , It is particularly preferably 10 to 90% by mass.

[Crosslinking system]

When using the said acrylic polymer which has the structural unit derived from the functional group containing monomer same as what is in an adhesive resin (I-1a), for example as an adhesive resin (I-2a), an adhesive composition (I-2) is You may contain a crosslinking agent further.

As said crosslinking agent in an adhesive composition (I-2), the thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and preferably 0.3 to 20 parts by mass, relative to 100 parts by mass of the adhesive resin (I-2a). It is especially preferable that it is -15 parts by mass.

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy energy rays such as ultraviolet rays.

As said photoinitiator in an adhesive composition (I-2), the thing similar to the photoinitiator in an adhesive composition (I-1) is mentioned.

As for the photoinitiator contained in the adhesive composition (I-2), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and more preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2a). It is especially preferable that it is -5 parts by mass.

[Other additives]

The pressure-sensitive adhesive composition (I-2) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention.

As said other additive in an adhesive composition (I-2), the thing similar to the other additives in an adhesive composition (I-1) is mentioned.

As for the other additives contained in the pressure-sensitive adhesive composition (I-2), only one type may be used, or two or more types thereof may be used, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

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

[menstruum]

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

As said solvent in an adhesive composition (I-2), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

The solvent contained in the pressure-sensitive adhesive composition (I-2) may be one type, or two or more types, and in the case of two or more types, combinations and ratios of these can be arbitrarily selected.

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

<Adhesive composition (I-3)>

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

In the pressure-sensitive adhesive composition (I-3), the content of the pressure-sensitive resin (I-2a) with respect to the total mass of components other than the solvent is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, It is particularly preferably 15 to 90% by mass.

[Energy ray curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays, and the pressure-sensitive adhesive composition (I-1) is contained. The same thing as the said energy ray curable compound can be mentioned.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). It is preferable, and it is particularly preferably 0.05 to 100 parts by mass.

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy energy rays such as ultraviolet rays.

As said photoinitiator in an adhesive composition (I-3), the thing similar to the photoinitiator in an adhesive composition (I-1) is mentioned.

As for the photoinitiator contained in the adhesive composition (I-3), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and preferably 0.03 to 10 parts by mass, relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. The denier is more preferable, and it is particularly preferably 0.05 to 5 parts by mass.

[Other additives]

The pressure-sensitive adhesive composition (I-3) may contain other additives that do not correspond to any of the components described above within a range that does not impair the effects of the present invention.

As said other additive, the thing similar to the other additive in an adhesive composition (I-1) is mentioned.

As for the other additives contained in the pressure-sensitive adhesive composition (I-3), only one kind may be used, or two or more kinds thereof may be used, and in the case of two or more kinds, combinations and ratios of these may be arbitrarily selected.

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

[menstruum]

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

As said solvent in an adhesive composition (I-3), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

As for the solvent contained in the adhesive composition (I-3), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

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

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

So far, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described, but the content of the components described above is the overall pressure-sensitive adhesive composition other than these three types of pressure-sensitive adhesive composition ( In this specification, it can be used similarly also in "we call it the adhesive composition other than adhesive composition (I-1)-(I-3)").

As the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive composition (I-1) to (I-3), in addition to the energy ray-curable pressure-sensitive adhesive composition, a non-energy ray curable pressure-sensitive adhesive composition is also exemplified.

Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy ray-curable pressure-sensitive adhesive resins (I-), such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin. The adhesive composition (I-4) containing 1a) is mentioned, and it is preferable to contain an acrylic resin.

It is preferable that the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive composition (I-1) to (I-3) contains one or more crosslinking agents, and the content thereof is the same as in the case of the pressure-sensitive adhesive composition (I-1) or the like. can do.

<Adhesive composition (I-4)>

As a preferable thing as an adhesive composition (I-4), what contains the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)]

As an adhesive resin (I-1a) in an adhesive composition (I-4), the thing similar to the adhesive resin (I-1a) in an adhesive composition (I-1) is mentioned.

As for the adhesive resin (I-1a) contained in the adhesive composition (I-4), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) with respect to the total mass of components other than the solvent is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, It is particularly preferably 15 to 90% by mass.

[Crosslinking system]

When using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from (meth)acrylic acid alkyl ester as the adhesive resin (I-1a), the adhesive composition (I-4) is additionally It is preferable to contain a crosslinking agent.

As a crosslinking agent in an adhesive composition (I-4), the thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 20 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferable that it is -15 parts by mass.

[Other additives]

The pressure-sensitive adhesive composition (I-4) may contain other additives that do not correspond to any of the components described above within a range that does not impair the effects of the present invention.

As said other additive, the thing similar to the other additive in an adhesive composition (I-1) is mentioned.

As for the other additives contained in the pressure-sensitive adhesive composition (I-4), only one kind may be used, or two or more kinds thereof may be used, and in the case of two or more kinds, combinations and ratios thereof may be arbitrarily selected.

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

[menstruum]

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

As said solvent in an adhesive composition (I-4), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

As for the solvent contained in the adhesive composition (I-4), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

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

In the composite sheet for forming a protective film, the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because, if the pressure-sensitive adhesive layer is energy ray-curable, it may not be possible to suppress curing of the pressure-sensitive adhesive layer at the same time when curing the film for forming a protective film by irradiation with energy rays. When the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the protective film-forming film and the pressure-sensitive adhesive layer after curing may be adhered to such an extent that they cannot be peeled off at their interfaces. In this case, it is difficult to peel the film for forming a protective film after curing, that is, a semiconductor chip (a semiconductor chip with a protective film) provided on the back surface from the support sheet provided with the pressure-sensitive adhesive layer after curing, so that the semiconductor chip with the protective film formed You will not be able to pick up normally. In the said support sheet, by making a pressure-sensitive adhesive layer non-energy-ray-curable, such a problem can be reliably avoided, and a semiconductor chip with a protective film can be picked up more easily.

Here, the effect in the case where the pressure-sensitive adhesive layer is non-energy ray curable has been described, but the same effect is provided if the layer directly in contact with the film for forming a protective film of the support sheet is a layer other than the pressure-sensitive adhesive layer, but this layer is non-energy ray curable. Indicates.

<<The manufacturing method of an adhesive composition>>

Pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3) such as pressure-sensitive adhesive compositions (I-1) to (I-3), pressure-sensitive adhesive compositions (I-4), the pressure-sensitive adhesive and, if necessary It is obtained by compounding each component for constituting an adhesive composition, such as components other than the said adhesive.

The order of addition when mixing each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, the solvent may be mixed with any other blending component other than the solvent to dilute the blending component in advance, or may be used without diluting any blending component other than the solvent in advance. You may use it by mixing with these compounding components.

The method of mixing each component when blending is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade or the like; A method of mixing using a mixer; You may select suitably from well-known methods, such as the method of adding and mixing ultrasonic waves.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Method of manufacturing a composite sheet for forming a protective film

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

For example, when manufacturing a support sheet, when laminating an adhesive layer on a base material, you may apply|coat the above-mentioned adhesive composition on a base material, and dry as needed.

On the other hand, for example, in the case of further laminating the film for forming a protective film on the pressure-sensitive adhesive layer laminated on the substrate, it is possible to directly coat the protective film-forming composition on the pressure-sensitive adhesive layer, thereby forming the protective film-forming film. . Layers other than the film for forming a protective film can also be laminated on the pressure-sensitive adhesive layer by the same method using a composition for forming this layer. As described above, when using one of the compositions to form a continuous two-layer stacked structure, it is possible to form a new layer by further coating the composition on the layer formed from the composition.

However, the layer to be laminated later among these two layers is previously formed using the composition on another release film, and the exposed surface of the formed layer on the opposite side to the side in contact with the release film is exposed to the remaining layer already formed. It is preferable to form a laminated structure of two consecutive layers by bonding with the surface. At this time, it is preferable that the composition is coated on the release treatment surface of the release film. The release film may be removed as necessary after formation of the laminated structure.

For example, a composite sheet for forming a protective film (a composite sheet for forming a protective film in which a support sheet is a laminate of a substrate and an adhesive layer) is produced by laminating an adhesive layer on a substrate and a film for forming a protective film laminated on the adhesive layer. In the case of a peeling film, the pressure-sensitive adhesive composition is coated on a substrate, and if necessary, dried, the pressure-sensitive adhesive layer is laminated on the substrate, and a protective film-forming composition is separately coated on the release film and dried as necessary. A film for forming a protective film is formed thereon. Then, the composite sheet for forming a protective film is obtained by bonding the exposed surface of the film for forming a protective film with the exposed surface of the pressure-sensitive adhesive layer laminated on a substrate, and laminating the film for forming a protective film on the pressure-sensitive adhesive layer.

On the other hand, in the case of laminating the pressure-sensitive adhesive layer on the substrate, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, as described above, by coating the pressure-sensitive adhesive composition on a release film and drying as necessary, on the release film An adhesive layer may be laminated|stacked on a base material by forming an adhesive layer and bonding the exposed surface of this layer with one surface of a base material.

In any of the methods, the release film may be removed at any timing after forming the target laminate structure.

In this way, all of the layers other than the base material constituting the composite sheet for forming a protective film are previously formed on the release film and can be laminated by a method of bonding to the surface of the target layer. The appropriate layer may be selected as appropriate to produce a composite sheet for forming a protective film.

On the other hand, the composite sheet for forming a protective film is usually stored in a state where a release film is pasted on the surface of the outermost layer (for example, the film for forming a protective film) on the opposite side to the support sheet. Therefore, by coating a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, on this release film (preferably, the release treatment surface), and drying it as necessary, the optimum release on the release film is performed. A layer constituting the surface layer is formed, and each remaining layer is laminated on the exposed surface opposite to the side in contact with the release film of this layer by any one of the methods described above, and bonded together without removing the release film. A composite sheet for forming a protective film can also be obtained by maintaining it.

◇Semiconductor chip manufacturing method

The film for forming a protective film and the composite sheet for forming a protective film can be used for the production of semiconductor chips.

As a method for manufacturing a semiconductor chip at this time, for example, a step of attaching a film for forming a protective film which does not constitute the composite sheet for forming a protective film or a film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer (hereinafter, It may abbreviate as "affixation process", and the process of forming a protective film by irradiating an energy ray to the film for protective film formation after sticking to the said semiconductor wafer (hereafter abbreviated as "protective film formation process") And a process of forming a modified layer inside the semiconductor wafer by irradiating laser light through the protective film or the film for forming a protective film so as to converge to a focus set inside the semiconductor wafer (hereinafter, referred to as “modified layer”). Forming process” and the semiconductor wafer on which the modified layer is formed, together with the protective film or the film for forming the protective film, in the surface direction (parallel to the surface) of the protective film or the film for forming a protective film. The process of obtaining a plurality of semiconductor chips by dividing the semiconductor wafer at the portion of the modified layer while expanding, cutting the protective film or the film for forming a protective film (hereinafter, may be abbreviated as "division process"). ).

Here, although the direction of the expansion of the semiconductor wafer is specified as the surface direction of the protective film or the film for forming a protective film, the surface direction is usually the same as the surface direction of the semiconductor wafer (for example, the direction of the back surface).

Hereinafter, the manufacturing method mentioned above is demonstrated, referring drawings. 7 to 9 are cross-sectional views schematically illustrating one embodiment of a method for manufacturing a semiconductor chip in the case of using a film for forming a protective film that does not constitute a composite sheet for forming a protective film. 10 to 12 are cross-sectional views for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a composite sheet for forming a protective film in which a film for forming a protective film is previously integrated with a support sheet is used.

<<The manufacturing method of a semiconductor chip when using the film for protective film formation which does not comprise the composite sheet for protective film formation>>

First, an embodiment of a manufacturing method in the case of using a film for forming a protective film that does not constitute a composite sheet for forming a protective film will be described taking an example where the film for forming a protective film is shown in FIG. 1 (this embodiment) May be referred to as "manufacturing method (1)-1").

In the above-mentioned attaching process of the manufacturing method (1)-1, as shown in Fig. 7(a), a film for forming a protective film on the back surface (opposite to the electrode formation surface) 9b of the semiconductor wafer 9 ( 13) is attached.

Here, when the 1st peeling film 151 is removed from the film 13 for protective film formation, and the 1st surface 13a of the film 13 for protective film formation is stuck to the back surface 9b of the semiconductor wafer 9 Is shown. Incidentally, in the semiconductor wafer 9, illustration of bumps and the like on the circuit surface is omitted.

After the affixing step of the manufacturing method (1)-1, in the protective film forming step, the energy ray is irradiated to the film 13 for forming a protective film after being affixed to the semiconductor wafer 9, and is shown in FIG. 7(b). As described, a protective film 13' is formed on the semiconductor wafer 9. The energy ray may be irradiated after removing the second release film 152 from the film 13 for forming a protective film.

Further, after the affixing step of the manufacturing method (1)-1, in the above-described modified layer forming step, the laser light is irradiated through the protective film 13' to converge to a focus set inside the semiconductor wafer 9, As shown in Fig. 7C, a modified layer 91 is formed inside the semiconductor wafer 9. The laser light is irradiated after removing the second release film 152 from the protective film 13'.

After the step of forming the modified layer in the manufacturing method (1)-1, prior to the dividing step, as shown in Fig. 7D, the surface on the side where the semiconductor wafer 9 of the protective film 13' is affixed ( In this specification, the support sheet (which may be referred to as the "first surface") (13a') is the opposite side surface (in this specification, the "second surface" may be referred to as) 13b') 10) is attached. The support sheet 10 is shown in FIG. 2 and the like, and is affixed to the protective film 13 ′ by the pressure-sensitive adhesive layer 12.

Subsequently, in the above-described dividing step of the manufacturing method (1)-1, the semiconductor wafer 9 on which the modified layer 91 is formed, together with the protective film 13', is the surface of the protective film 13' (first surface ( 13a') or expand in the second surface 13b') direction, cut the protective film 13', and divide the semiconductor wafer 9 at the portion of the modifying layer 91, as shown in FIG. As shown in (e), a plurality of semiconductor chips 9'is obtained. At this time, the protective film 13' is cut (divided) at a position along the periphery of the semiconductor chip 9'. The protective film 13' after cutting is denoted by 130'.

In the dividing step, a force (tensile force) is applied in this direction by expanding (expanding) the semiconductor wafer 9 and the protective film 13' in the direction indicated by the arrow I in Fig. 7(d) to apply the semiconductor wafer 9 ) And the protective film 13' are divided.

By the above, the target semiconductor chip 9'is obtained as a semiconductor chip on which a protective film is formed.

On the other hand, Fig. 7 shows a case where the support sheet 10 is attached to the protective film 13' after performing the protective film forming step and the modified layer forming step. However, in the manufacturing method (1)-1, after attaching the support sheet 10 to the film 13 for protective film formation, you may perform a protective film formation process and a modified layer formation process, and after a protective film formation process, a protective film ( After attaching the support sheet 10 to 13'), you may perform a modified layer formation process.

In the manufacturing method (1)-1, by using the film 13 for forming a protective film, in the above-described dividing step, when the semiconductor wafer 9 is divided into a semiconductor chip 9', the protective film 13' Alternatively, lifting of the semiconductor chip 9'from the protective film 130' after cutting can be suppressed.

In the manufacturing method (1)-1, a modified layer forming step is performed after the protective film forming step, but in the method of manufacturing a semiconductor chip according to the present embodiment, a protective film forming step may be performed after the modified layer forming step (this embodiment) The form may be referred to as "manufacturing method (1)-2").

8 is a cross-sectional view schematically illustrating one embodiment of a method for manufacturing such a semiconductor chip.

In the pasting step of the manufacturing method (1)-2, as in the case of the manufacturing method (1)-1, as shown in Fig. 8A, a protective film is formed on the back surface 9b of the semiconductor wafer 9 The dragon film 13 is affixed.

After the affixing step of the manufacturing method (1)-2, in the above-described modified layer forming step, the laser light is irradiated through the protective film forming film 13 so as to converge to a focus set inside the semiconductor wafer 9, As shown in Fig. 8B, a modified layer 91 is formed inside the semiconductor wafer 9. The laser light is irradiated after removing the second release film 152 from the film 13 for forming a protective film.

In addition, after the affixing step of the manufacturing method (1)-2, in the protective film forming step, the energy ray is irradiated to the protective film forming film 13 after being affixed to the semiconductor wafer 9, and Fig. 8(c) As shown in the figure, a protective film 13' is formed on the semiconductor wafer 9. By performing this step, a semiconductor wafer having a protective film in the same state as in Fig. 7C is obtained after the step of forming the modified layer in the manufacturing method (1)-1.

Thereafter, as shown in Figs. 8(d) to 8(e), as in the case of the manufacturing method (1)-1 (as shown in Figs. 7(d) to 7(e)) ), the support sheet 10 is affixed to the second surface 13b' of the protective film 13', and then, by performing the above-described dividing step, the protective film 13' is cut and the modified layer 91 is formed. By dividing the semiconductor wafer 9 at the portion of, a plurality of semiconductor chips 9'is obtained.

By the above, the target semiconductor chip 9'is obtained as a semiconductor chip on which a protective film is formed.

On the other hand, in FIG. 8, the case where the support sheet 10 is attached to the protective film 13' after performing a modified layer formation process and a protective film formation process is shown. However, in manufacturing method (1)-2, after attaching the support sheet 10 to the film 13 for protective film formation, you may perform a modified layer formation process and a protective film formation process, and after a modified layer formation process, a protective film After attaching the support sheet 10 to the film 13 for forming, you may perform a protective film formation process.

Also in the manufacturing method (1)-2, by using the film 13 for forming a protective film, in the dividing step, when the semiconductor wafer 9 is divided into a semiconductor chip 9', the protective film 13' Alternatively, lifting of the semiconductor chip 9'from the protective film 130' after cutting can be suppressed.

In the manufacturing methods (1)-1 and (1)-2, the division step is performed after the protective film forming step, but in the method of manufacturing the semiconductor chip according to the present embodiment, the division step is performed without the protective film forming step. You may perform a protective film formation process after a division process (this embodiment may be called "manufacturing method (1)-3").

9 is a cross-sectional view schematically illustrating one embodiment of a method for manufacturing such a semiconductor chip.

As shown in Figs. 9(a) to 9(b), the affixing step and the modifying layer forming step of the manufacturing method (1)-3 are the affixing step and the modifying layer forming step of the manufacturing method (1)-2. It can be carried out in the same manner as (as shown in Figs. 8A to 8B).

After the step of forming the modified layer in the manufacturing method (1)-3, prior to the division step, as shown in Fig. 9(c), the support sheet 10 is applied to the second surface 13b of the film 13 for forming a protective film. ).

Subsequently, in the above-described dividing step of the manufacturing method (1)-3, the semiconductor wafer 9 on which the modified layer 91 was formed, together with the film 13 for forming a protective film, and the surface of the film 13 for forming a protective film ( Expanded in the direction of the first surface 13a or the second surface 13b, the protective film forming film 13 is cut, and the semiconductor wafer 9 is divided at the portion of the modified layer 91 , As shown in Fig. 9D, a plurality of semiconductor chips 9'is obtained. At this time, the film 13 for forming a protective film is cut (divided) at a position along the periphery of the semiconductor chip 9'. The film 13 for forming a protective film after cutting is denoted by reference numeral 130.

In the dividing step, the semiconductor wafer 9 and the semiconductor wafer 9 to which a force (tensile force) was applied in this direction by expanding (expanding) the semiconductor wafer 9 and the film 13 for forming a protective film in the direction indicated by the arrow I in Fig. 9C. 9) and the film 13 for forming a protective film are divided.

By the above, the target semiconductor chip 9'is obtained as a semiconductor chip on which a film for forming a protective film is formed.

On the other hand, Fig. 9 shows a case in which the support sheet 10 is attached to the film 13 for forming a protective film after the step of forming the modified layer. However, in the manufacturing method (1)-3, after attaching the support sheet 10 to the film 13 for film formation, you may perform a modified layer formation process.

In the manufacturing method (1)-3, by using the film 13 for forming a protective film, in the dividing step, when the semiconductor wafer 9 is divided into a semiconductor chip 9', the film for forming a protective film ( 13) Alternatively, lifting of the semiconductor chip 9'from the film 130 for forming a protective film after cutting can be suppressed.

In the manufacturing method (1)-3, after the dividing step, an energy ray is irradiated to the film 130 for forming a protective film via the support sheet 10, and as shown in Fig. 9(e), the semiconductor chip A protective film 130' may be formed on (9').

In FIG. 9(e), the case where the protective film 130' is formed before pickup of the semiconductor chip 9'is formed, but the formation of the protective film 130' is after pickup of the semiconductor chip 9', etc. It can be performed at any timing after the dividing step.

<<The manufacturing method of a semiconductor chip when using the composite sheet for protective film formation in which the film for protective film formation was previously integrated with the support sheet>

Next, an embodiment of the manufacturing method in the case of using a composite sheet for forming a protective film in which the film for forming a protective film is previously integrated with a support sheet will be described as an example in which the composite sheet for forming a protective film is shown in FIG. 2 as an example. (This embodiment may be referred to as "manufacturing method (2)-1").

In the above-mentioned attaching process of the manufacturing method (2)-1, as shown in Fig. 10(a), a film for forming a protective film in a composite sheet 1A for forming a protective film on the back surface 9b of the semiconductor wafer 9 ( 13) is attached. The composite sheet 1A for forming a protective film is used by removing the release film 15.

After the affixing step of the manufacturing method (2)-1, in the protective film forming step, energy rays are irradiated to the protective film forming film 13 after being affixed to the semiconductor wafer 9, and shown in FIG. 10(b). As described, a protective film 13' is formed on the semiconductor wafer 9. At this time, the energy ray is irradiated to the film 13 for forming a protective film via the support sheet 10.

On the other hand, here, the composite sheet for forming a protective film after the film 13 for forming a protective film becomes the protective film 13' is denoted by 1A'. This is the same in the subsequent diagrams.

In addition, after the affixing step of the manufacturing method (2)-1, in the above-described modified layer forming step, a protective film 13' (a composite sheet for forming a protective film 1A' is provided so as to converge to a focus set inside the semiconductor wafer 9. A laser beam is irradiated via )) to form a modified layer 91 inside the semiconductor wafer 9, as shown in Fig. 10C.

Subsequently, in the above-described dividing step of the manufacturing method (2)-1, the semiconductor wafer 9 on which the modified layer 91 is formed, together with the protective film 13', is the surface of the protective film 13' (first surface ( 13a') or expanded in the second surface 13b') direction, the protective film 13' is cut, and the semiconductor wafer 9 is divided at the portion of the modified layer 91, and is shown in FIG. As shown in (d), a plurality of semiconductor chips 9'is obtained. At this time, the protective film 13' is cut (divided) at a position along the periphery of the semiconductor chip 9'to become the protective film 130'.

In the dividing step, a force (tensile force) is applied in this direction by expanding (expanding) the semiconductor wafer 9 and the protective film 13' in the direction indicated by arrow I in FIG. ) And the protective film 13' are divided.

By the above, the target semiconductor chip 9'is obtained as a semiconductor chip on which a protective film is formed.

In the manufacturing method (2)-1, by using the film 13 for forming a protective film, in the above-described dividing step, when the semiconductor wafer 9 is divided into a semiconductor chip 9', the protective film 13' Alternatively, lifting of the semiconductor chip 9'from the protective film 130' after cutting can be suppressed.

In the manufacturing method (2)-1, a modified layer forming step is performed after the protective film forming step, but in the method of manufacturing a semiconductor chip according to the present embodiment, a protective film forming step may be performed after the modified layer forming step (this embodiment) The form may be referred to as "manufacturing method (2)-2").

11 is a cross-sectional view schematically illustrating one embodiment of a method for manufacturing such a semiconductor chip.

In the manufacturing method (2)-2, as in the case of the manufacturing method (2)-1, as shown in Fig. 11A, a composite sheet for forming a protective film is formed on the back surface 9b of the semiconductor wafer 9 The film 13 for forming a protective film in (1A) is affixed.

After the affixing step of the manufacturing method (2)-2, in the above-described modified layer forming step, a film 13 for forming a protective film (a composite sheet for forming a protective film 1A) so as to converge to a focus set inside the semiconductor wafer 9 A laser beam is irradiated through) to form a modified layer 91 inside the semiconductor wafer 9, as shown in Fig. 11B.

In addition, after the affixing process of the manufacturing method (2)-2, in the above-mentioned protective film forming process, energy rays are irradiated to the film 13 for forming a protective film after being affixed to the semiconductor wafer 9, and Fig. 11(c) As shown in the figure, a protective film 13' is formed on the semiconductor wafer 9. By performing this step, a semiconductor wafer having a protective film in the same state as in Fig. 10(c) is obtained after the step of forming the modified layer in the manufacturing method (2)-1.

After that, as shown in Fig. 11(d), by performing the above-described dividing step in the same manner as in the manufacturing method (2)-1 (as shown in Fig. 10(d)), the protective film 13' While cutting, the semiconductor wafer 9 is divided at the site of the modified layer 91 to obtain a plurality of semiconductor chips 9'.

By the above, the target semiconductor chip 9'is obtained as a semiconductor chip on which a protective film is formed.

Also in the manufacturing method (2)-2, by using the film 13 for forming a protective film, in the above-described dividing step, when the semiconductor wafer 9 is divided into a semiconductor chip 9', the protective film 13' Alternatively, lifting of the semiconductor chip 9'from the protective film 130' after cutting can be suppressed.

In the manufacturing methods (2)-1 and (2)-2, the division step is performed after the protective film formation step, but in the method of manufacturing the semiconductor chip according to the present embodiment, the division step is performed without the protective film formation step. You may perform a protective film formation process after a division process (this embodiment may be called "manufacturing method (2)-3").

12 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing such a semiconductor chip.

As shown in Figs. 12(a) to 12(b), the affixing step and the modifying layer forming step of the manufacturing method (2)-3 are the affixing step and the modifying layer forming step of the manufacturing method (2)-2. It can be carried out in the same manner as (shown in Figs. 11A to 11B).

Subsequently, in the above-described dividing step of the manufacturing method (2)-3, the semiconductor wafer 9 on which the modified layer 91 was formed, together with the film 13 for forming a protective film, and the surface of the film 13 for forming a protective film ( Expanded in the direction of the first surface 13a or the second surface 13b, the protective film forming film 13 is cut, and the semiconductor wafer 9 is divided at the portion of the modified layer 91 , As shown in Fig. 12C, a plurality of semiconductor chips 9'is obtained. At this time, the film 13 for forming a protective film is cut (divided) at a position along the periphery of the semiconductor chip 9'.

In the dividing step, a force (tensile force) is applied in this direction by expanding (expanding) the semiconductor wafer 9 and the film 13 for forming a protective film in the direction indicated by the arrow I in FIG. (9) and the film 13 for forming a protective film are divided.

By the above, the target semiconductor chip 9'is obtained as a semiconductor chip on which a film for forming a protective film is formed.

In the manufacturing method (2)-3, by using the film 13 for forming a protective film, in the dividing step, when the semiconductor wafer 9 is divided into a semiconductor chip 9', the film for forming a protective film ( 13) Alternatively, lifting of the semiconductor chip 9'from the film 130 for forming a protective film after cutting can be suppressed.

In the manufacturing method (2)-3, after the dividing step, the energy film is irradiated to the film 130 for forming a protective film, and as shown in Fig. 12D, the protective film 130' is placed on the semiconductor wafer 9. ).

In FIG. 12(d), the case where the protective film 130' is formed before the semiconductor chip 9'is picked up, but the formation of the protective film 130' is after the semiconductor chip 9'is picked up, etc. It can be performed at any timing after the dividing step.

Up to this point, the method of manufacturing a semiconductor chip in the case of using the film 13 for forming a protective film shown in FIG. 1, the support sheet 10 shown in FIG. 2, and the composite sheet 1A for forming a protective film shown in FIG. 2 has been described. , The method for manufacturing a semiconductor chip of the present invention is not limited to these.

For example, when a composite sheet for forming a protective film is used, the composite sheet for forming a protective film (1B) to (1E) shown in FIGS. 3 to 6, a composite sheet for forming a protective film further comprising the intermediate layer, and the like, Even if other than the composite sheet 1A for forming a protective film shown in FIG. 2 is used, a semiconductor chip can be similarly produced.

In addition, the semiconductor chip can be manufactured in the same manner even if a support sheet 10 other than the support sheet 10 shown in Fig. 2 is used, such as that described above, which consists of only a base material or that an intermediate layer is laminated.

As described above, in the case of using the composite sheet for forming a protective film or the support sheet of another embodiment, based on the difference in the structure of these sheets, in the above-described manufacturing method, the process is appropriately added, changed, deleted, etc., A semiconductor chip can be manufactured.

◇Semiconductor device manufacturing method

After the semiconductor chip is obtained by the above-described manufacturing method, the semiconductor chip is picked up from the support sheet while the protective film after division is attached (that is, as a semiconductor chip on which the protective film is formed) and is picked up (not shown).

Thereafter, the semiconductor chip of the semiconductor chip on which the obtained protective film is formed is flip-chip connected to the circuit surface of the substrate in the same manner as in the conventional method, and then a semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package (not shown).

As one aspect of the present invention, the film for forming a protective film is an energy ray curable film for forming a protective film, and the adhesion between the film for forming a protective film and a silicon wafer when the film for forming a protective film is measured by the following method is 3.6 N/25. It has a property of ㎜ or more and 8N/25㎜ or less, and the film for forming a protective film is irradiated with ultraviolet light to form a protective film, and the shear strength of the protective film when measured by the following method is 11N/3㎜□ or more and 13N/3㎜□ or less The film for forming a protective film has the properties of, and the film for forming a protective film includes a compound having a carboxyl group or a carboxyl group forming a salt and a polymerizable group.

Adhesion between protective film forming film and silicon wafer:

After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film was measured from, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer.

Shear strength of the protective film:

After attaching the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet rays under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film, thereby protecting the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film.

The compound may be an aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester.

The compound may be mono succinate (2-acryloyloxyethyl).

As another aspect of the present invention, the film for forming a protective film is an energy ray curable protective film forming film, and the film for forming a protective film is an energy ray curable component (a2), ε-caprolactone modified tris (2-acryloxyethyl) iso Cyanurate (content: 5 to 15% by mass relative to the total mass of the solid content of the protective film-forming composition (IV-1)); As a polymer (b) that does not have an energy ray-curable group, an acrylic polymer (content: protective film forming composition (IV-1)) formed by copolymerizing methyl acrylate (85 parts by mass) and acrylic acid 2-hydroxyethyl (15 parts by mass) 25 to 30% by mass relative to the total mass of solids); As the photopolymerization initiator (c), the total mass of solid content of 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (content: composition for forming a protective film (IV-1)) To 0.3 to 1% by mass); As a filler (d), silica filler (content: 50-65 mass% with respect to the total mass of the solid content of the composition (IV-1) for forming a protective film); As a coupling agent (e), 3-methacryloxypropyl trimethoxysilane (content: 0.2-0.6 mass% with respect to the total mass of the solid content of the protective film forming composition (IV-1)); As a coloring agent (g), with respect to the total mass of the solid content of the phthalocyanine blue pigment, isoindolinone yellow pigment, and anthraquinone red pigment and styrene acrylic resin (content: the composition for forming a protective film (IV-1)) 2 to 6% by mass); As compound (p), a compound having a carboxyl group or a group in which the carboxyl group forms a salt and a polymerizable group (content: 0.15 to 3% by mass based on the total mass of the solid content of the composition for forming a protective film (IV-1), more preferably 0.25 to 1% by mass) (however, the total content of each component does not exceed 100% by mass relative to the total mass of the solid content of the protective film-forming composition (IV-1)).

When the film for forming a protective film is measured by the following method, the adhesive force between the film for forming a protective film and a silicon wafer has a property of 3.6 N/25 mm or more and 8 N/25 mm or less, and the protective film forming film is irradiated with ultraviolet light. The film for forming a protective film has a property that the protective film has a shear strength of 11 N/3 mm□ or more and 13 N/3 mm□ or less when measured by the following method, and the film for forming a protective film has a carboxy group or a carboxy group. It includes a compound having a group and a polymerizable group.

Adhesion between protective film forming film and silicon wafer:

After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film was measured from, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer.

Shear strength of the protective film:

After attaching the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet rays under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film, thereby protecting the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film.

The compound may be an aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester.

The compound may be mono succinate (2-acryloyloxyethyl).

As another aspect of the present invention, the silicon chip on which the protective film is formed includes a protective film that is a cured product of a film for forming an energy ray-curable protective film and a film for forming the protective film, and includes a silicon chip that is a cut product of a silicon wafer. The adhesive strength between the film for forming a protective film before curing and the silicon wafer is 3.6 N/25 mm or more and 8 N/25 mm or less, and the shear strength of the protective film when measured by the following method is 11 N/3 mm□ or more and 13 N/3 ㎜□ or less.

Adhesion between protective film forming film and silicon wafer:

After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film was measured from, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer.

Shear strength of the protective film:

After attaching the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet rays under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film, thereby protecting the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film.

The film for forming a protective film includes a compound having a carboxyl group or a carboxyl group forming a salt and a polymerizable group.

The compound may be an aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester.

The compound may be mono succinate (2-acryloyloxyethyl).

As another aspect of the present invention, a silicon wafer on which a film for forming a protective film is formed includes a film for forming an energy ray curable protective film and a silicon wafer on which the film for forming a protective film is attached, and a film for forming a protective film when measured by the following method. The adhesive strength between the wafer and the silicon wafer is 3.6 N/25 mm or more and 8 N/25 mm or less, and the film for forming a protective film is irradiated with ultraviolet light to form a protective film, and the shear strength of the protective film when measured by the following method is 11 N/3 mm. The film for forming a protective film has a property of □ or more and 13N/3㎜ or less.

Adhesion between protective film forming film and silicon wafer:

After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film was measured from, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer.

Shear strength of the protective film:

After attaching the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet rays under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film, thereby protecting the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film.

The film for forming a protective film includes a compound having a carboxyl group or a carboxyl group forming a salt and a polymerizable group.

The compound may be an aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester.

The compound may be mono succinate (2-acryloyloxyethyl).

Example

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

<Manufacturing raw material for composition for forming a protective film>

The raw materials used for the preparation of the composition for forming a protective film are shown below.

[Energy ray-curable component (a2)]

(a2)-1: ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Industries, Trifunctional UV-curable compound)

[Polymer (b) having no energy ray-curable groups]

(b)-1: Acrylic polymer (weight average molecular weight 300000, glass transition temperature) obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass) 6°C).

[Photopolymerization initiator (c)]

(c)-1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone ("Irgacure (registered trademark) 369" manufactured by BASF))

[Filling material (d)]

(d)-1: Silica filler (melted quartz filler, average particle diameter 8 µm)

[Coupling agent (e)]

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

[Colorant (g)]

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

[Compound (p)]

(p)-1: Mono succinate (2-acryloyloxyethyl).

[Example 1]

<Production of a composite sheet for forming a protective film>

(Preparation of composition for forming a protective film (IV-1))

Energy ray-curable component ((a2)-1), polymer ((b)-1), photopolymerization initiator ((c)-1), filler ((d)-1), coupling agent ((e)-1), The coloring agents ((g)-1) and the compound ((p)-1) were dissolved or dispersed in methyl ethyl ketone so that their contents (solid content, parts by mass) were the values shown in Table 1, and stirred at 23°C. Thereby, the composition (IV-1) for forming a protective film having a solid content concentration of 50% by mass was prepared. On the other hand, the description of "-" in the content of a component in Table 1 means that the composition (IV-1) for forming a protective film does not contain the component.

(Preparation of adhesive composition (I-4))

Contains an acrylic polymer (100 parts by mass, solids) and an isocyanate-based crosslinking agent ("Coronate L" manufactured by Nippon Polyurethane, a tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solids). A non-energy ray-curable pressure-sensitive adhesive composition (I-4) having a solid content concentration of 30% by mass containing methyl ethyl ketone as a solvent was prepared. The acrylic polymer has a weight average molecular weight of 600000 by copolymerizing 2-ethylhexyl methacrylate (80 parts by mass) and HEA (20 parts by mass).

(Production of support sheet)

The pressure-sensitive adhesive composition (I-4) obtained above was coated on the release-treated surface of a release film ("SP-PET381031" manufactured by Lintec, thickness 38 mu m) on which one side of a polyethylene terephthalate film was peeled off by a silicone treatment. Then, by heating and drying at 120° C. for 2 minutes, a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 μm was formed.

Subsequently, by attaching a polypropylene-based film (80 µm thick) as a base material to the exposed surface of the pressure-sensitive adhesive layer, a support sheet made of a base material, a pressure-sensitive adhesive layer, and a release film laminated in these thickness directions in this order was obtained.

(Production of a composite sheet for forming a protective film)

The protective film forming composition obtained above on the said peeling-treated surface of the peeling film (2nd peeling film, "SP-PET382150" by Lintec, thickness 38 micrometers) in which one surface of the polyethylene terephthalate film was peeled by silicone treatment By coating (IV-1) and drying at 100° C. for 2 minutes, a film for forming an energy ray-curable protective film having a thickness of 25 μm was prepared.

Further, by peeling the peeling treatment surface of the peeling film (first peeling film, "SP-PET381031" manufactured by Lintec, thickness: 38 µm) on the exposed surface of the obtained protective film-forming film on the side without the second peeling film , A laminated film having a first release film on one surface of the film for forming a protective film and a second release film on the other surface was obtained.

Next, the release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above. Moreover, the 1st peeling film was removed from the laminated film obtained above. Then, by bonding the exposed surface of the pressure-sensitive adhesive layer formed by removing the release film and the exposed surface of the film for forming a protective film formed by removing the first release film, the base material, the pressure-sensitive adhesive layer, the film for forming a protective film, and the second release film In this order, a composite sheet for forming a protective film that was laminated in these thickness directions was produced.

<Evaluation of the film for forming a protective film>

(Adhesive force between the film for forming a protective film and the silicon wafer)

The 1st peeling film was removed from the laminated film obtained above, and the adhesive tape ("D-841" by Lintec) was attached to the exposed surface of the film for protective film formation thereby. Then, by cutting the obtained one to a size of 25 mm × 140 mm, a test piece was produced.

Subsequently, from the film for forming a protective film of the obtained test piece, the second release film was removed, and the exposed surface of the film for forming a protective film thus formed was affixed to a #2000 polished surface of a 6-inch silicon wafer (300 µm thick), for 30 minutes. Politics.

Subsequently, under the condition of 23° C., a laminate of a film for forming a protective film and a pressure-sensitive adhesive tape from the silicon wafer using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation) The so-called 180° peeling was performed to peel at a peeling rate of 300 mm/min so that the surfaces contacting each other had an angle of 180°. Then, the peeling force (load, N/25 mm) at this time was measured, and this measurement value was taken as the adhesive force between the film for forming a protective film and the silicon wafer. Table 1 shows the results.

<Evaluation of the protective film>

(Suppression of lifting of semiconductor chips)

The first release film was removed from the laminated film obtained above, and the exposed surface of the resulting film for forming a protective film was adhered to a #2000 polished surface of an 8-inch silicon wafer (300 µm thick).

Next, the 2nd peeling film was removed from this film for protective film formation, and the film for protective film formation was exposed. Moreover, the peeling film was removed from the adhesive layer of the support sheet obtained above, and the adhesive layer was exposed. Then, by bonding the exposed surface of the pressure-sensitive adhesive layer to the exposed surface of the film for forming a protective film and attaching it to the ring frame, the base material, the pressure-sensitive adhesive layer, the film for forming a protective film and the silicon wafer are in this order, in their thickness direction. The stacked laminate was fixed to the ring frame and left for 30 minutes.

Subsequently, by using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec) under conditions of roughness of 195 Pa/cm 2 and light intensity of 170 mJ/cm 2, the protective film forming film was irradiated with ultraviolet light through the substrate and the adhesive layer. , The film for forming a protective film was cured to obtain a protective film. Hereafter, what was obtained by this, that is, the film for protective film formation in the said laminated body became a protective film, is called "the laminated body after hardening."

Subsequently, the laminate and the ring frame after curing were installed on a laser saw ("DFL7361" manufactured by Disco Corporation) while controlling the positions of the laminate and the ring frame after curing so that the laser beam could be irradiated onto the silicon wafer through a protective film.

Subsequently, a laser beam having a wavelength of 1342 nm was irradiated through a support sheet and a protective film to converge to a focus set inside the silicon wafer, thereby forming a modified layer inside the silicon wafer.

Subsequently, the cured laminate and ring frame were installed on a die separator ("DDS2300" manufactured by Disco), and under the condition of 0 DEG C, the cured laminate was extruded in the surface direction (direction along the surface) of the protective film. By cutting, the protective film was cut, and a silicon wafer was divided at the modified layer site to obtain a plurality of silicon chips having a size of 3 mm x 3 mm.

Subsequently, the state of division of the obtained silicon chip on the protective film was visually observed, and when there is no silicon chip having any excitation from the protective film, it is determined as "A", and the excitation from the protective film is generated. When there is more than one chip, it was judged as "B". Table 1 shows the results.

(Shear strength of the protective film)

Except for using a 6-inch silicon wafer (300 µm thick) instead of an 8-inch silicon wafer (300 µm thick), in the same manner as in the evaluation of “suppression of floating of semiconductor chips”, for forming a substrate, an adhesive layer, and a protective film In this order, a laminate formed of films and silicon wafers laminated in their thickness direction was fixed to a ring frame, and left standing for 30 minutes. On the other hand, the film for forming a protective film was affixed to a #2000 polished surface of a 6-inch silicon wafer.

Subsequently, by using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec) under conditions of roughness of 195 Pa/cm 2 and light intensity of 170 mJ/cm 2, the protective film forming film was irradiated with ultraviolet light through the substrate and the adhesive layer. , The protective film-forming film was cured to obtain a protective film to obtain a silicon wafer on which the protective film was formed.

Next, using a dicing blade, the silicon wafer is diced into a protective film (dicing a silicon wafer on which a protective film is formed) and reorganized to form a silicon chip (a silicon having a protective film formed thereon) having a protective film having a size of 3 mm×3 mm. Chip).

Subsequently, using a universal bond tester ("DAGE4000" manufactured by Nordson Advanced Technology) under the conditions of 23 DEG C, the protective film of the protective film is formed only among the silicon chips in which the protective film was formed at a rate of 200 µm/s by a share tool. Force was applied in the direction of the surface. Then, the maximum value of the force applied until the protective film was destroyed was checked, and this was set as the shear strength (N/3 mm□). Table 1 shows the results.

<Production of a composite sheet for forming a protective film, and evaluation of the film and protective film for forming a protective film>

[Example 2, Comparative Example 1]

In the same manner as in Example 1, a film for forming a protective film and a composite sheet for forming a protective film were prepared in the same manner as in Example 1, except that the amount of the blended components in the production of the protective film forming composition (IV-1) was shown in Table 1. Then, the film for protective film formation and the protective film were evaluated. Table 1 shows the results.

As is apparent from the above results, in Examples 1 to 2, when the silicon wafer on which the protective film was formed is expanded, the protective film is cut, and when the silicon wafer is divided into a silicon chip, the silicon chip from the protective film is lifted. It was suppressed. In Examples 1 to 2, the adhesive force between the film for forming a protective film and the silicon wafer was as high as 3.8 N/25 mm or more (3.8 to 4.5 N/25 mm). Further, in Examples 1 to 2, the shear strength of the protective film was greater than 11.3 N/3 mm□ or higher (11.3 to 11.4 N/3 mm□).

In contrast, in Comparative Example 1, the excitation of the silicon chip from the protective film was not suppressed. In Comparative Example 1, the adhesive force between the film for forming a protective film and the silicon wafer was 2.6 N/25 mm, which was lower than Examples 1-2. In Comparative Example 1, the shear strength of the protective film was 10.1 N/3 mm□, which was smaller than Examples 1 to 2.

From the results of these Examples and Comparative Examples, it was clearly confirmed that the presence or absence of the excitation of the silicon chip was affected by the above-described adhesive strength and shear strength.

The present invention can be used in the manufacture of semiconductor devices.

1A, 1A', 1B, 1C, 1D, 1E... composite sheet for forming a protective film, 10... support sheet, 10a... surface of the support sheet (first side), 11... substrate, 11a... ··············································································································· Film for forming, 13a, 23a... surface of film for forming a protective film (first surface), 13b... surface of film for forming a protective film (second surface), 13'... protective film, 130'... Protective film after cutting, 15... peeling film, 151... 1st peeling film, 152... 2nd peeling film, 16... adhesive layer for jig, 16a... surface of adhesive layer for jig, 9 Semi-conductor wafer, 9b... Back side of semiconductor wafer, 91...Modified layer of semiconductor wafer, 9'... Semi-conductor chip

Claims (3)

As a film for forming an energy ray curable protective film,
The adhesive force between the film for forming a protective film and the silicon wafer measured by the following method is 3 N/25 mm or more,
When the protective film-forming film is irradiated with ultraviolet light to form a protective film, the protective film-forming film having a shear strength of 10.5 N/3 mm□ or more measured by the following method:
Adhesion between protective film forming film and silicon wafer:
After affixing the film for forming a protective film having a thickness of 25 μm to a silicon wafer, the silicon wafer at a peeling rate of 300 mm/min is formed so that an angle of 180° is formed between the film for forming a protective film and the surfaces in contact with each other of the silicon wafer. The peeling force (N/25 mm) when peeling the film for forming a protective film from was measured, and the measured value was taken as the adhesive force between the film for forming a protective film and the silicon wafer;
Shear strength of the protective film:
After attaching the film for forming a protective film having a thickness of 25 µm to a silicon wafer, the film for forming a protective film is irradiated with ultraviolet light under conditions of roughness 195 Pa/cm 2 and a light amount of 170 mJ/cm 2 to cure the film for forming a protective film to protect the film The silicon wafer on which the obtained protective film was formed was diced to obtain a silicon chip on which a protective film having a size of 3 mm x 3 mm was formed, and the surface of the protective film at a rate of 200 µm/s only in the protective film among the silicon chips on which the obtained protective film was formed. A force is applied in the direction, and the maximum value (N/3 mm□) of the force applied until the protective film is destroyed is taken as the shear strength of the protective film. A composite sheet for forming a protective film comprising a support sheet and comprising the film for forming a protective film of claim 1 on the support sheet. A step of attaching the film for forming a protective film in the film for forming a protective film of claim 1 or a composite sheet for forming a protective film of claim 2 to a semiconductor wafer,
A step of forming a protective film by irradiating an energy ray to the film for forming a protective film after being attached to the semiconductor wafer;
A step of forming a modified layer inside the semiconductor wafer by irradiating laser light through the protective film or the film for forming a protective film to converge to a focus set inside the semiconductor wafer;
The semiconductor wafer on which the modified layer is formed is expanded with the protective film or the film for forming a protective film in the surface direction of the protective film or the film for forming a protective film, and the film for forming the protective film or the protective film is cut, and the modified A method of manufacturing a semiconductor chip having a step of dividing the semiconductor wafer at a layer portion to obtain a plurality of semiconductor chips.

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