KR20210041496A - Film for protective film formation and composite sheet for protective film formation - Google Patents

Abstract

The present invention provides a film for forming a protective film for forming a protective film on the back surface of a chip, in which utilizing the maximum value (X_max) of absorbance of the protective film at a wavelength of 1400-1500 nm and the specific heat (S_150) of the protective film at 150℃, Z_150 calculated by the formula Z_150 = X_max/S_150 is 0.38 or more, and utilizing the X_max and the specific heat (S_200) of the protective film at 200℃, Z_200 calculated by the formula Z_200 = X_max/S_200 is 0.33 or more. Also provided is a composite sheet for forming a protective film, which is provided with a support sheet and the film for forming a protective film provided on one surface of the support sheet.

Description

Protective film forming film and protective film forming composite sheet {FILM FOR PROTECTIVE FILM FORMATION AND COMPOSITE SHEET FOR PROTECTIVE FILM FORMATION}

The present invention relates to a protective film-forming film and a protective film-forming composite sheet. This application claims priority based on Japanese Patent Application No. 2019-184718 for which it applied to Japan on October 7, 2019, and uses the content here.

In wafers such as semiconductor wafers and insulator wafers, a circuit is formed on one surface (circuit surface) of the wafer, and some have protruding electrodes such as bumps on the surface (circuit surface). Such wafers are divided into chips, and the protruding electrodes are connected to connection pads on the circuit board, thereby being mounted on the circuit board.

In such a wafer or chip, in order to suppress breakage such as occurrence of cracks, the surface (rear surface) opposite to the circuit surface is sometimes protected with a protective film (refer to Patent Documents 1 to 2).

In order to form such a protective film, a film for forming a protective film for forming a protective film is affixed on the back surface of a semiconductor wafer, and at this time, a support sheet and a film for forming a protective film formed on one side of the support sheet are provided. A composite sheet for forming a protective film can be used. The support sheet can be used as a dicing sheet for fixing the wafer when dividing a film for forming a protective film or a wafer having a protective film on the back surface into chips.

Japanese Unexamined Patent Publication No. 2015-32644 International Publication No. 2015/146936

As described above, the circuit board on which the chip is mounted is used for various electronic components as a substrate device, but by improving the electrical connection strength between the protruding electrode of the chip and the connection pad on the circuit board, a more reliable substrate device can be manufactured. I can.

On the other hand, in Patent Documents 1 to 2, no means for further improving such connection strength is disclosed.

The present invention is a composite sheet for forming a protective film comprising a protective film forming film for forming a protective film on the back surface of a chip, and the protective film forming film, wherein the electrical connection strength between the protruding electrode of the chip and the connection pad on the circuit board It aims to provide what makes improvement possible.

The present invention is a film for forming a protective film for forming a protective film on the back surface of a chip, the maximum value (X _max ) of the absorbance at a wavelength of 1400 to 1500 nm of the protective film, and the specific heat (S) of the protective film at 150°C. ₁₅₀ ), using the equation:

Z ₁₅₀ ＝X _max ／S ₁₅₀

_{Z 150} calculated by is 0.38 or more, and,

Using the X _max and the specific heat at 200° C. of the protective film (S ₂₀₀ ), the formula:

Z ₂₀₀ ＝X _max ／S ₂₀₀

A film for forming a protective film in which Z _{200 calculated by is 0.33 or more is provided.}

The film for forming a protective film of the present invention may be thermosetting or energy ray curable.

The film for forming a protective film of the present invention may contain two or more light absorbers capable of absorbing either or both of visible light and infrared light.

The film for forming a protective film of the present invention may contain a carbon material.

_{In the film for forming a protective film of the present invention, it is preferable that the minimum value (T m} ) of the transmittance of light having a wavelength of 400 to 750 nm of the protective film is 15% or less.

_{In the film for forming a protective film of the present invention, it is preferable that the maximum value (U m} ) of the reflectance of light having a wavelength of 1400 to 1500 nm of the protective film is 20% or less.

The present invention provides a support sheet and a protective film-forming film formed on one side of the support sheet, wherein the protective film-forming film is the protective film-forming film of the present invention.

In the composite sheet for forming a protective film of the present invention, the support sheet includes a substrate and an adhesive layer formed on one side of the substrate, and the adhesive layer is disposed between the substrate and the film for forming a protective film. You may have it.

According to the present invention, a protective film-forming film for forming a protective film on the back surface of a chip, and a protective film-forming composite sheet comprising the protective film-forming film, wherein the protruding electrode of the chip and the connection pad on the circuit board are electrically connected What makes it possible to improve the strength is provided.

1 is a cross-sectional view schematically showing an example of a film for forming a protective film according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film according to an embodiment of the present invention.
4 is a cross-sectional view schematically showing still another example of a composite sheet for forming a protective film according to an embodiment of the present invention.
5 is a cross-sectional view schematically showing still another example of the composite sheet for forming a protective film according to an embodiment of the present invention.
6 is a cross-sectional view schematically showing an example of a connection state between a chip on which a protective film is formed and a circuit board when the film for forming a protective film according to an embodiment of the present invention is used.

◇ Film for forming a protective film

The film for forming a protective film according to an embodiment of the present invention is a film for forming a protective film for forming a protective film on the back surface of a chip, the maximum value (X _max ) of the absorbance at a wavelength of 1400 to 1500 nm of the protective film, _{Using the specific heat (S 150} ) at 150° C. of the protective film, the formula:

Z ₁₅₀ ＝X _max ／S ₁₅₀

_{Z 150} calculated by is 0.38 or more, and,

Using the X _max and the specific heat at 200° C. of the protective film (S ₂₀₀ ), the formula:

Z ₂₀₀ ＝X _max ／S ₂₀₀

_{Z 200} calculated by is 0.33 or more.

The film for protective film formation of this embodiment can constitute a composite sheet for protective film formation by laminating it with a support sheet, for example, as described later.

The film for protective film formation of this embodiment is a film used to protect a chip by forming a protective film on the back surface of a chip.

The film for forming a protective film is soft and can be affixed to a wafer before being divided into chips.

The film for forming a protective film of the present embodiment may be curable or non-curable. In other words, the film for forming a protective film may function as a protective film by its curing, or may function as a protective film in an uncured state.

The film for curable protective film formation may be any of thermosetting and energy ray curing properties, and may have properties of both thermosetting and energy ray curing properties.

In this specification, the "energy ray" means having both energy among electromagnetic waves or charged particle rays. Examples of energy rays include ultraviolet rays, radiation, and electron rays. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet source. The electron beam can be irradiated with what is generated by an electron beam accelerator or the like.

In addition, in this specification, "energy ray hardenability" means a property which hardens by irradiation of energy rays, and "non-energy ray hardenability" means a property which does not harden even when irradiating energy rays.

In addition, "non-curable" means a property that is not cured by any means such as heating or irradiation with energy rays. The film for forming a non-curable protective film is regarded as a protective film after the step formed on the target object.

In the present specification, the "wafer" refers to a semiconductor wafer made of elemental semiconductors such as silicon, germanium, and selenium, or compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; Insulator wafers made of insulators such as sapphire and glass are mentioned.

A circuit is formed on one surface of these wafers, and in this specification, the surface of the wafer on the side where the circuit is formed is referred to as a "circuit surface". In addition, the side surface opposite to the circuit surface of the wafer is referred to as "the back side".

The wafer is divided into chips by means of dicing or the like. In this specification, as in the case of a wafer, the surface of the chip on the side on which the circuit is formed is referred to as "circuit surface", and the surface of the chip opposite to the circuit surface is referred to as "back surface".

On both the circuit surface of the wafer and the circuit surface of the chip, protruding electrodes such as bumps and fillers are formed. It is preferable that the protruding electrode is made of solder.

By using the film for forming a protective film of the present embodiment or a composite sheet for forming a protective film provided with the same, a chip having a protective film on the back surface (in this specification, it may be referred to as a ``chip with a protective film'') can be produced. I can.

Further, by using the chip on which the protective film is formed, a substrate device can be manufactured.

In this specification, the "substrate device" means that a chip on which a protective film is formed is formed by flip-chip connection to a connection pad on a circuit board in a protruding electrode on the circuit surface thereof. For example, when a semiconductor wafer is used as the wafer, a semiconductor device is exemplified as the substrate device.

In the manufacturing process of the substrate device, by heating the circuit board on which the chip with the protective film is mounted using a reflow furnace equipped with a halogen heater, the protruding electrode on the chip on which the protective film is formed is melted, and the protruding electrode and the circuit board In some cases, the electrical connection of the upper connection pads is strengthened.

In the protective film obtained from the film for forming a protective film of the present embodiment, Z ₁₅₀ is 0.38 or more, and Z ₂₀₀ is 0.33 or more, so that the absorption amount of near-infrared rays is large during the heating, and the temperature during heating is higher than usual. For this reason, by the action of this protective film which became higher temperature, the protruding electrode on the chip on which the protective film was formed also became higher temperature, and the protruding electrode was easily melted under the influence, and consequently, the protruding electrode and the circuit board were The electrical connection strength of the connection pad becomes stronger than usual.

By using a circuit board on which such a chip is mounted, it is possible to manufacture a more highly reliable substrate device.

_{Z 150} (=X _max /S ₁₅₀ ) of the protective film is an index indicating the easiness of increasing the temperature of the protective film at 150°C, and is 0.38 or more, for example, 0.41 or more, 0.45 or more, 0.55 or more, 0.65 or more, 0.8 Any one of 1.2 or more, 1.5 or more, 2 or more, and 2.5 or more may be sufficient. When Z ₁₅₀ is equal to or greater than the lower limit, the electrical connection strength between the protruding electrode and the connection pad on the circuit board becomes stronger.

The upper limit of Z ₁₅₀ is not particularly limited. From the point that the formation of the protective film satisfying the above conditions of _{Z 150 is easier, it is preferable that Z 150} is 4.2 or less.

Z ₁₅₀ can be appropriately adjusted within a range set by arbitrarily combining any one of the lower and upper limits described above. For example, in one embodiment, Z ₁₅₀ is preferably 0.38 to 4.2, for example, 0.41 to 4.2, 0.45 to 4.2, 0.55 to 4.2, 0.65 to 4.2, 0.8 to 4.2, 1.2 to 4.2, 1.5 Any one of -4.2, 2-4.2, and 2.5-4.2 may be sufficient. However, these are examples of _{Z 150.}

_{Z 200} (=X _max /S ₂₀₀ ) of the protective film is an index indicating the ease of temperature rise of the protective film at 200°C, and is preferably 0.33 or more, preferably 0.35 or more, for example, 0.4 or more, 0.45 or more, or 0.52. Above, 0.6 or more, 0.8 or more, 1.2 or more, 1.4 or more, 1.9 or more, and any one of 2.4 or more may be sufficient. When Z ₂₀₀ is equal to or greater than the lower limit, the electrical connection strength between the protruding electrode and the connection pad on the circuit board becomes stronger.

The upper limit of Z ₂₀₀ is not particularly limited. Z ₂₀₀ is preferably 4 or less from the viewpoint of easier formation of a protective film that satisfies the above conditions of Z _200.

Z ₂₀₀ can be appropriately adjusted within a range set by arbitrarily combining any one of the lower and upper limits described above. For example, in one embodiment, Z ₂₀₀ is preferably 0.33 to 4, more preferably 0.35 to 4, for example, 0.4 to 4, 0.45 to 4, 0.52 to 4, 0.6 to 4, Any one of 0.8-4, 1.2-4, 1.4-4, 1.9-4, and 2.4-4 may be sufficient. However, these are examples of _{Z 200.}

The reason for specifying the protective film-forming film of this embodiment by using the specific heat at 150°C and 200°C of the protective film is that when heating the circuit board on which the chip on which the protective film is formed is heated, it is heated to a high temperature of 250°C or higher. In that case, this is because the chip on which the protective film is formed necessarily passes through heating at a temperature of 150°C and 200°C.

_{The maximum value (X max} ) of the absorbance at a wavelength of 1400 to 1500 nm of the protective film is not particularly limited as long as the conditions of _{Z 150} and Z _{200 are satisfied.}

X _max is preferably 0.4 or more, more preferably 0.5 or more, and may be, for example, any one of 0.6 or more, 0.9 or more, 1.2 or more, 1.6 or more, 2 or more, 2.4 or more, and 2.8 or more.

It is preferable that X _max is 4.5 or less, and for example, any one of 3.5 or less, 2.5 or less, 2 or less, 1.5 or less, 1.4 or less, 1.2 or less, and 0.99 or less may be sufficient. _{The protective film} with X max equal to or less than the upper limit is more easily formed, and when near-infrared rays are irradiated, only the surface of the irradiated area and its vicinity are rapidly heated, and as a result, the surface of the irradiated area is discolored or roughened. It can highly suppress the phenomenon of becoming cotton.

X _max can be appropriately adjusted within a range set by arbitrarily combining any one lower limit value and any one upper limit value described above. For example, in one embodiment, X _max is preferably 0.4 to 4.5, more preferably 0.5 to 4.5, for example, 0.6 to 4.5, 0.9 to 4.5, 1.2 to 4.5, 1.6 to 4.5, Any one of 2 to 4.5, 2.4 to 4.5, and 2.8 to 4.5 may be used, and in one embodiment, it is preferably 0.4 to 4.5, for example, 0.4 to 3.5, 0.4 to 2.5, 0.4 to 2, 0.4 to Any one of 1.5, 0.4 to 1.4, 0.4 to 1.2, and 0.4 to 0.99 may be used. However, these are examples of _{X max.}

_{The specific heat (S 150} ) of the protective film at 150° C. is not particularly limited as long as the condition of _{Z 150 is satisfied.}

S ₁₅₀ is preferably 1 or more, more preferably 1.1 or more, and may be, for example, 1.2 or more.

S ₁₅₀ is preferably 2 or less, more preferably 1.9 or less, further preferably 1.8 or less, particularly preferably 1.7 or less, and may be, for example, 1.65 or less.

S ₁₅₀ can be appropriately adjusted within a range set by arbitrarily combining any one lower limit value and any one upper limit value described above. For example, in one embodiment, S ₁₅₀ is preferably 1 to 2, more preferably 1 to 1.9, still more preferably 1 to 1.8, particularly preferably 1 to 1.7, for example For example, it may be 1 to 1.65. However, these are examples of _{S 150.}

_{The specific heat (S 200} ) of the protective film at 200° C. is not particularly limited as long as the condition of _{Z 200 is satisfied.}

S ₂₀₀ is preferably 1.1 or more, more preferably 1.2 or more, and may be, for example, 1.3 or more.

S ₂₀₀ is preferably 2.1 or less, more preferably 2 or less, still more preferably 1.9 or less, particularly preferably 1.8 or less, and may be, for example, 1.75 or less.

S ₂₀₀ can be appropriately adjusted within a range set by arbitrarily combining any one lower limit value and any one upper limit value described above. For example, in one embodiment, S ₂₀₀ is preferably 1.1 to 2.1, more preferably 1.1 to 2, further preferably 1.1 to 1.9, particularly preferably 1.1 to 1.8, for example For example, it may be 1.1 to 1.75. However, these are examples of _{S 200.}

S ₁₅₀ and S ₂₀₀ can be calculated from the measured values of the differential scanning calorific value of the protective film obtained by using a differential scanning calorimeter in accordance with JIS K 7123:2012 and setting the temperature increase rate to 10° C./min.

_{The minimum value (T m} ) of the transmittance of light having a wavelength of 400 to 750 nm of the protective film is not particularly limited, but is preferably 15% or less, more preferably 10% or less, even more preferably 7% or less, and 4% or less. It is particularly preferred. When T _m is equal to or less than the above upper limit, the presence or absence of the protective film becomes more easily visually recognizable.

The lower limit of T _m is not particularly limited, and for example, T _m may be 0% or more.

_{The maximum value (U m} ) of the reflectance of light having a wavelength of 1400 to 1500 nm of the protective film is not particularly limited, but it is preferably 20% or less, more preferably 15% or less, and still more preferably 12% or less. When U _m is equal to or less than the above upper limit, when the circuit board on which the chip on which the above-described protective film is formed is mounted is heated, the temperature of the protective film can be easily increased. Further, when a chip on which a protective film is formed is used, it is possible to suppress malfunction of a device using near infrared rays such as a near infrared reflection sensor.

The lower limit of U _m is not particularly limited, and for example, U _m may be 0% or more. From the point that the formation of the protective film satisfying the above conditions of _{U m is easier, it is preferable that U m} is 0.2% or more, more preferably 0.5% or more, and even more preferably 1% or more.

The reflectance of light of the protective film can be measured by the method described in Examples to be described later.

In the present embodiment, _{the protective film defining the above-described X max} , S ₁₅₀ and S ₂₀₀ is preferably a cured product obtained by heating the protective film forming film at 145° C. for 2 hours when the protective film forming film is thermosetting. When the film for forming a protective film is energy ray-curable, it is preferably a cured product obtained by irradiating the film for forming a protective film with energy rays twice under conditions of an illuminance of 280 mW/cm 2 and an amount of light of 260 mJ/cm 2.

On the other hand, when the film for forming a protective film is non-curable, the protective film _{defining the above-described X max} , S ₁₅₀ and S ₂₀₀ is the film itself for forming a protective film.

In this embodiment, when _{calculating Z 150} mentioned above, as X _max and S ₁₅₀ , what was measured using the same type of protective film is adopted. Similarly, when the above-described Z ₂₀₀ is calculated, as X _max and S ₂₀₀ , those measured using the same type of protective film are employed.

In the case of forming a protective film by thermally curing the protective film forming film, unlike the case of curing by irradiation with energy rays, the protective film-forming film is sufficiently cured by heating even when its thickness is thickened. Can be formed. Further, by using a common heating means such as a heating oven, it is possible to collectively heat and heat cure a large number of films for forming a protective film.

In the case of forming a protective film by curing the protective film-forming film by irradiation with energy rays, unlike the case of thermosetting, the composite sheet for forming a protective film does not need to have heat resistance, and constitutes a wide range of composite sheets for forming a protective film. can do. Further, it can be cured in a short time by irradiation with energy rays.

When the film for forming a protective film is not cured and used as a protective film, since the curing step can be omitted, a chip on which the protective film is formed can be manufactured in a simplified step.

It is preferable that the film for forming a protective film is thermosetting or energy ray-curable.

Regardless of whether the film for forming a protective film is curable or non-curable, and when curable, regardless of whether it is thermosetting or energy ray-curable, the film for forming a protective film may consist of one layer (single layer), It may consist of a plurality of layers of two or more layers. When the film for protective film formation consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not specifically limited.

When the film for forming a protective film is composed of two or more layers, the adhesion between the layers is poor, or the protective film is warped based on the difference in the ease of stretching and contracting of each layer, and the protective film is peeled off from the back surface of the chip. There is a possibility that a problem may occur, and it is preferable that the film for forming a protective film consists of one layer from the viewpoint of suppressing such a problem.

In the present 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 the layers may be the same, all layers may be different, and only some of the layers may be the same." It means "to become", and "the multiple layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer are different from each other".

Regardless of whether the film for forming a protective film is curable or non-curable, and when curable, regardless of whether it is thermosetting or energy ray-curable, the thickness of the protective film-forming film is preferably 1 to 100 μm, and 3 It is more preferable that it is -80 micrometers, and it is especially preferable that it is 5-60 micrometers, For example, any one of 10-50 micrometers, 15-40 micrometers, 17-38 micrometers, and 20-30 micrometers may be sufficient. When the thickness of the protective film-forming film is greater than or equal to the above lower limit, a protective film having a higher protective ability can be formed, and it is easier to form a protective film having a high absorbance. When the thickness of the protective film-forming film is equal to or less than the above upper limit, excessive thickness can be avoided, and the temperature of the protective film at the time of temperature rise can be easily conducted to the chip.

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

<<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, the film for forming a protective film can be formed by coating the composition for forming a protective film on the surface to be formed and drying as necessary. The content ratio between components that do not vaporize at room temperature in the composition for forming a protective film is usually the same as the content ratio between the components in the film for forming a protective film. In the present specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, an ordinary temperature, and examples thereof include a temperature of 15 to 25°C.

The film for forming a thermosetting protective film can be formed using a composition for forming a thermosetting protective film, the film for forming an energy ray-curable protective film can be formed using a composition for forming an energy ray-curable protective film, and the film for forming a non-curable protective film is non-curable. It can be formed using a composition for forming a chemical conversion protective film. On the other hand, in the present specification, when the protective film-forming film has both thermosetting and energy ray-curable properties, when the contribution of the thermosetting of the protective film-forming film to the formation of the protective film is greater than that of the energy ray curing, The film for forming a protective film is treated as being thermosetting. Conversely, with respect to the formation of the protective film, when the contribution of the energy ray curing of the protective film-forming film is greater than that of the thermal curing, the protective film-forming film is treated as energy ray curing.

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

The drying conditions of the composition for forming a protective film are not particularly limited regardless of whether the film for forming a protective film is curable or non-curable, and when curable, regardless of whether it is thermosetting or energy ray-curable. However, when the composition for forming a protective film contains a solvent described later, it is preferable to heat-dry it. In addition, the composition for forming a protective film containing a solvent is preferably heated and dried at 70 to 130°C for 10 seconds to 5 minutes. However, the composition for forming a thermosetting protective film is preferably heated and dried so that the composition itself and the film for forming a thermosetting protective film formed from the composition are not thermally cured.

Hereinafter, a film for forming a thermosetting protective film, a film for forming an energy ray-curable protective film, and a film for forming a non-curable protective film will be sequentially described.

◎ Film for forming a thermosetting protective film

The curing conditions when forming the protective film by thermosetting the thermosetting protective film-forming film are not particularly limited as long as the curing degree is such that the protective film sufficiently exhibits its function, and if appropriately selected according to the type of the thermosetting protective film-forming film do.

For example, the heating temperature during thermosetting of the thermosetting protective film-forming film is preferably 100 to 200°C, more preferably 110 to 170°C, and particularly preferably 120 to 150°C. Further, the heating time during the thermal curing is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.

It is preferable that the protective film after formation by thermal curing is slowly cooled to room temperature. The slow cooling method is not particularly limited and may be left to cool.

The film for forming a protective film after heating and cooling is obtained by heating the film for forming a protective film at room temperature until it reaches a temperature exceeding the room temperature, and then cooling it until it reaches the room temperature, thereby forming a film for forming a protective film after heating and cooling, and the rigidity of the film for forming a protective film after heating and cooling. When the hardness of the film for forming a protective film before heating is compared at the same temperature, when the film for forming a protective film after heating and cooling is firm, the film for forming a protective film is thermosetting.

Preferred films for forming a thermosetting protective film include, for example, those containing a polymer component (A), a thermosetting component (B), and a light absorbing agent (I).

The polymer component (A) is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component capable of curing (polymerization) reaction using heat as a trigger of the reaction. In addition, in this specification, a polycondensation reaction is also included in a polymerization reaction.

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

Preferred compositions for forming a thermosetting protective film include, for example, a composition for forming a thermosetting protective film (III-1) containing the polymer component (A), a thermosetting component (B) and a light absorber (I) (in this specification, simply It may be abbreviated as "composition (III-1)"), etc. are mentioned.

[Polymer component (A)]

The polymer component (A) is a component for imparting film-forming properties, flexibility, toughness, electrical ductility, and the like to the film for forming a thermosetting protective film, and imparting flexibility, toughness, and malleability to the protective film.

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

Examples of the polymer component (A) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins, and acrylic resins are preferable.

As said acrylic resin in polymer component (A), a well-known acrylic polymer is mentioned.

It is preferable that it is 10000-2000000, and, as for the weight average molecular weight (Mw) of an acrylic resin, it is more preferable that it is 100000-1500000. When the weight average molecular weight of the acrylic resin is equal to or greater than the above lower limit, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. In addition, when the weight average molecular weight of the acrylic resin is less than or equal to the above upper limit, the film for forming a thermosetting protective film is easier to follow on the uneven surface of the adherend, and the occurrence of voids between the adherend and the film for forming a thermosetting protective film is more suppressed. .

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

It is preferable that it is -60 to 70 degreeC, and, as for the glass transition temperature (Tg) of an acrylic resin, it is more preferable that it is -30 to 50 degreeC. When the Tg of the acrylic resin is equal to or greater than the lower limit, for example, the adhesion between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability of the support sheet is appropriately improved. Further, when the Tg of the acrylic resin is equal to or less than the above upper limit, the adhesion between the thermosetting protective film-forming film and the cured product to the adherend is improved.

The acrylic resin has m types (m is an integer greater than or equal to 2) constituent units, and to m types of monomers that induce these constituent units, any one non-overlapping number from 1 to m is sequentially assigned, and , When named as "monomer m", the glass transition temperature (Tg) of an acrylic resin can be calculated using the formula of Fox shown below.

(Wherein, Tg is the glass transition temperature of the acrylic resin; m is an integer of 2 or more; Tg _k is the glass transition temperature of the homopolymer of the monomer m; W _k is the structural unit derived from the monomer m in the acrylic resin. is the mass fraction of m, provided that W _k satisfies the following formula)

(In the formula, m and W _k are the same as above)

As the Tg _k , a value described in a polymer data handbook, an adhesive handbook, or a polymer handbook may be used. _{For example, the Tg k} of the homopolymer of methyl acrylate is 10°C, the Tg _k of the homopolymer of methyl methacrylate is 105°C, and the Tg _k of the homopolymer of 2-hydroxyethyl acrylate is -15°C.

Examples of the acrylic resin include polymers of one or two or more (meth)acrylic acid esters; One or two or more (meth)acrylic acid esters and one or two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide, etc. Coalescence, etc. are mentioned.

Examples of the (meth)acrylic acid ester constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n- (meth)acrylate. Butyl, (meth) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate, pentyl (meth) acrylate, (meth) heptyl acrylate, (meth) acrylate 2-ethyl Hexyl, (meth) acrylate isooctyl, (meth) acrylate n-octyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, (meth) acrylate, (meth) acrylate, (meth) acrylate Dodecyl ((meth) acrylate lauryl), (meth) acrylate tridecyl, (meth) acrylate tetradecyl ((meth) acrylate myristylus), (meth) acrylate pentadecyl, (meth) acrylate hexadecyl ((meth) Alkyl groups constituting alkyl esters such as palmityl acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate ((meth) acrylate stearyl) are alkyl (meth)acrylates having a chain structure having 1 to 18 carbon atoms. ester;

(Meth)acrylate cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;

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

(Meth) acrylate cycloalkenyl ester, such as (meth) acrylate dicyclopentenyl ester;

(Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylate dicyclopentenyloxyethyl ester;

Imide (meth)acrylate;

Glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth) ) Hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylate;

And substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylate. Here, the "substituted amino group" means a group obtained by substituting one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.

The number of monomers constituting the acrylic resin may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The acrylic resin may have a functional group capable of bonding with other compounds such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) to be described later, or may be directly bonded to another compound without a crosslinking agent (F). When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the composite sheet for forming a protective film tends to be improved.

In the present invention, as the polymer component (A), a thermoplastic resin other than acrylic resin (hereinafter, simply abbreviated as ``thermoplastic resin'' in some cases) may be used alone without using an acrylic resin, or used in combination with an acrylic resin. You can do it. By using the thermoplastic resin, the peelability of the protective film from the supporting sheet is improved, or the film for forming a thermosetting protective film is easily followed on the uneven surface of the adherend, and voids, etc. are generated between the adherend and the film for forming a thermosetting protective film. It may be suppressed more than this.

It is preferable that it is 1000-100000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3000-80000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably -30 to 150°C, more preferably -20 to 120°C.

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

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

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the polymer component to the total mass of the film for forming a thermosetting protective film in the film for forming a thermosetting protective film) The content ratio of (A)) is preferably 5 to 80% by mass, more preferably 8 to 70% by mass, even more preferably 11 to 60% by mass, regardless of the type of the polymer component (A). , It is particularly preferably 14 to 50% by mass, and for example, any one of 17 to 45% by mass and 20 to 40% by mass may be used.

Since the protective film-forming film and the protective film are usually thin, in the case of using a protective film or protective film having low toughness and weakness, a crack (gap) occurs in the protective film-forming film or protective film during the manufacture of a chip with a protective film formed thereon. do. In that case, when the chip on which the finally manufactured protective film is formed is heated, there is a possibility that the heat transfer effect from the high-temperature protective film to the protruding electrode on the chip may be lowered. However, when the ratio is greater than or equal to the lower limit, the toughness of the protective film-forming film and the protective film is higher, and the effect of suppressing such a problem is enhanced.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is the polymer component (A) and the thermosetting component It is considered to contain (B).

[Thermosetting component (B)]

The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film.

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

Examples of the thermosetting component (B) include an epoxy thermosetting resin, a polyimide resin, and an unsaturated polyester resin, and an epoxy thermosetting resin is preferred.

(Epoxy thermosetting resin)

The epoxy-based thermosetting resin consists of an epoxy resin (B1) and a thermosetting agent (B2).

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

Epoxy resin (B1)

Examples of the epoxy resin (B1) include known ones, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ethers and their hydrogenated products, orthocresol novolac epoxy resins, dicyclopenta Diene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher epoxy compounds.

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

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

Further, examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth)acrylamide group, and the like, Acryloyl groups are preferred.

Although the number average molecular weight of the epoxy resin (B1) is not particularly limited, it is preferably 300 to 30,000, more preferably 300 to 10000 in terms of curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the cured protective film. And it is particularly preferably 300 to 3000.

The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g/eq, more preferably 150 to 950 g/eq.

As for the epoxy resin (B1), 1 type may be used individually, 2 or more types may be used together, and when 2 or more types are used together, these combinations and ratios can be selected arbitrarily.

·Heat curing agent (B2)

The thermal curing agent (B2) functions as a curing agent for the epoxy resin (B1).

Examples of the thermosetting agent (B2) include a compound having two or more functional groups capable of reacting with an epoxy group per molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group in which an acid group is anhydride, and the like, and a phenolic hydroxyl group, an amino group, or an acid group is preferably an anhydride group. It is more preferable that it is a hydroxyl group or an amino group.

Among the thermal curing agents (B2), examples of the phenol curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins. have.

Among the thermal curing agents (B2), examples of the amine curing agent having an amino group include dicyandiamide.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.

Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30,000, It is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Among the thermosetting agents (B2), 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.

The thermosetting agent (B2) may be used singly or in combination of two or more, and when two or more of them are used in combination, combinations and ratios thereof can be arbitrarily selected.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, and 0.1 to 200 parts by mass based on 100 parts by mass of the epoxy resin (B1). It is more preferable, it is still more preferable that it is 0.1-100 mass parts, and it is especially preferable that it is 0.5-50 mass parts, For example, even if it is any one of 0.5-25 mass parts, 0.5-10 mass parts, and 0.5-5 mass parts do. When the content of the thermosetting agent (B2) is equal to or greater than the lower limit, the curing of the film for forming a thermosetting protective film is more likely to proceed. When the content of the thermosetting agent (B2) is less than or equal to the upper limit, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is the polymer component (A). It is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and, for example, any one of 30 to 100 parts by mass, 40 to 80 parts by mass, and 50 to 70 parts by mass based on 100 parts by mass of the content. Can also be done. When the content of the thermosetting component (B) is within such a range, for example, the adhesion between the cured product of the film for forming a protective film and the support sheet is suppressed, and the peelability of the support sheet is improved.

[Light absorber (I)]

The light absorbing agent (I) is a component that absorbs light in a state in which it is present in the protective film, thereby facilitating an increase in temperature of the protective film.

When the composition (III-1) and the film for forming a thermosetting protective film contain the light absorbing agent (I), X _max of the protective film becomes larger, and it becomes easier to _{increase Z 150} and Z _200. Further, since the transmittance of light having a wavelength of 400 to 750 nm of the protective film becomes small, the presence or absence of the protective film can be easily visually recognized.

Examples of the light absorbing agent (I) include organic pigments and inorganic pigments.

Examples of the organic pigments include dimonium pigments, aluminum pigments, cyanine pigments, merocyanine pigments, chromonium pigments, squarylium pigments, azrenium pigments, polymethine pigments, naphthoqui Non-based pigments, pyryllium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments Dye, isoindolinone dye, quinophthalone dye, pyrrole dye, thioindigo dye, metal complex dye (metal complex dye), dithiol metal complex dye, indolephenol dye, triarylmethane dye , Anthraquinone-based dyes, dioxazine-based dyes, naphthol-based dyes, azomethine-based dyes, benzimidazolone-based dyes, spirone-based dyes, pyrantrone-based dyes, and srene-based dyes.

Examples of the inorganic pigment include carbon materials such as carbon black; Lanthanum materials; Tin-based materials; Antimony-based materials; And tungsten-based materials. Here, the lanthanum-based material, tin-based material, antimony-based material, and tungsten-based material mean a material containing lanthanum, a material containing tin, a material containing antimony, and a material containing tungsten, respectively.

Among these, the inorganic pigment is preferably a carbon material, and more preferably carbon black, from the viewpoint of relatively excellent dispersibility and less deterioration of itself due to heat.

It is preferable that the light absorber (I) is capable of absorbing either or both of visible light and infrared light.

The composition (III-1) and the light absorbing agent (I) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. For example, the composition (III-1) and the film for forming a thermosetting protective film may contain only one or two or more types of organic pigments as the light absorbing agent (I), and may contain only one or two or more types of inorganic pigments. , An organic dye and an inorganic pigment may be contained together 1 type or 2 or more types.

The composition (III-1) and the film for forming a thermosetting protective film preferably contain two or more types of light absorbers (I) capable of absorbing either or both of visible light and infrared light, and more preferably contain 2 to 7 types.

When the composition (III-1) and the film for forming a thermosetting protective film contain an inorganic pigment as the light absorbing agent (I), it is preferable to contain a carbon material, and in that case, for example, a carbon material and an organic dye are contained together. You can do it.

In the composition (III-1), the ratio of the content of the light absorbing agent (I) to the total content of all components other than the solvent (that is, the light absorbing agent to the total mass of the film for forming a thermosetting protective film in The content ratio of (I)) is preferably 0.1 to 20% by mass, more preferably 0.3 to 17.5% by mass, still more preferably 0.5 to 16% by mass, and particularly preferably 1 to 15% by mass. Do. When the ratio is greater than or equal to the lower limit, the effect of using the light absorbing agent (I) is more remarkably obtained. When the ratio is less than or equal to the upper limit, excessive use of the light absorbing agent (I) is suppressed.

[Hardening accelerator (C)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).

Preferred curing accelerators (C) include 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, 2-phenyl-4-methyl-5 Imidazoles such as hydroxymethylimidazole (imidazole in which at least one hydrogen atom is substituted with a group other than a hydrogen atom); Organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphine in which at least one hydrogen atom is substituted with an organic group); Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and triphenyl phosphine tetraphenyl borate, etc. are mentioned.

The composition (III-1) and the curing accelerator (C) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using the curing accelerator (C), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the curing accelerator (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the content of the thermosetting component (B). It is preferable that it is negative, and it is more preferable that it is 0.1-7 mass parts. When the content of the curing accelerator (C) is more than the lower limit, the effect of using the curing accelerator (C) is more remarkably obtained. When the content of the curing accelerator (C) is less than or equal to the above upper limit, for example, the high polarity curing accelerator (C) moves to the adhesive interface side with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions and segregates. The inhibitory effect increases. As a result, the reliability of the chip with the protective film obtained by using the composite sheet for forming a protective film is further improved.

[Filling material (D)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). Since the thermosetting protective film-forming film contains the filler (D), the thermosetting protective film-forming film and its cured product (i.e., the protective film) facilitate adjustment of the thermal expansion coefficient, and by optimizing this thermal expansion coefficient for the object to be formed of the protective film. , The reliability of the chip on which the protective film is formed obtained by using the composite sheet for forming a protective film is further improved. Further, when the film for forming a thermosetting protective film contains the filler (D), the moisture absorption rate of the protective film may be reduced or the heat dissipation property may be improved.

Although any of an organic filler and an inorganic filler may be sufficient as the filler (D), it is preferable that it is an inorganic filler.

Preferred inorganic fillers include powders such as silica, stainless steel, 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; Glass fiber, etc. are mentioned.

Among these, the inorganic filler is preferably silica, alumina, or stainless steel. When alumina is used _{, adjustment of S 150} and S ₂₀₀ of the protective film becomes easier, and when insulation is required for the protective film, it becomes easier to impart insulation to the protective film. When stainless steel is used _{, adjustment of S 150} and S ₂₀₀ of the protective film becomes particularly easy.

Although the average particle diameter of the filler (D) is not particularly limited, it is preferably 10 to 4000 nm, and more preferably 30 to 3500 nm. When the average particle diameter of the filler (D) is within such a range, the effect of using the filler (D) is more remarkably obtained.

For example, it is possible to easily increase the amount of the filler (D) in the composition (III-1) and the film for forming a thermosetting protective film, and in that it becomes easier to control _{S 150 and S 200 of the protective film, the filler (} The average particle diameter of D) is preferably 10 to 2500 nm, more preferably 20 to 1000 nm, and still more preferably 30 to 600 nm.

On the other hand, in any case, the filler (D) having an average particle diameter equal to or greater than the above lower limit has good handleability, and therefore, the quality of the composition (III-1) is stabilized and the effect of using the protective film is stably obtained. Do.

On the other hand, it indicates the value of the "average particle diameter" means a particle diameter (D ₅₀₎ of from 50% integrated value of the particle size distribution curve determined according to the laser diffraction scattering method, unless otherwise stated in the specification.

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

When using the filler (D), in the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, for forming a thermosetting protective film in a film for forming a thermosetting protective film) The content ratio of the filler (D) to the total mass of the film) is preferably 15 to 75% by mass, more preferably 18 to 70% by mass, for example, 45 to 70% by mass and 50 to 70% by mass. Any one of mass% and 60 to 70 mass% may be used. When the ratio is within such a range, it becomes easier to adjust the thermal expansion coefficient of the film for forming a thermosetting protective film and the cured product (ie, the protective film), and to control S ₁₅₀ and S _{200 of the protective film.}

[Coupling agent (E)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesion of the film for forming a thermosetting protective film to an adherend can be improved. Further, by using the coupling agent (E), the cured product of the film for forming a thermosetting protective film does not impair heat resistance and improves water resistance.

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

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyltrimethoxysilane. Cidyloxymethyldiethoxysilane, 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 (III-1) and the coupling agent (E) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When a coupling agent (E) is used, in the composition (III-1) and the film for forming a thermosetting protective film, the content of the coupling agent (E) is 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). Relatively, it is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and particularly preferably 0.1 to 2 parts by mass. When the content of the coupling agent (E) is equal to or greater than the lower limit, the use of the coupling agent (E), such as improving the dispersibility of the filler (D) in the resin, or improving the adhesion to the adherend of the film for forming a thermosetting protective film. The effect is obtained more remarkably. In addition, when the content of the coupling agent (E) is equal to or less than the upper limit, generation of outgas is further suppressed.

[Crosslinking agent (F)]

When using a polymer component (A) having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, which can be bonded to other compounds such as the above-described acrylic resin, is used, the composition (III- 1) and the film for thermosetting protective film formation may contain a crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking by bonding the functional group in the polymer component (A) with another compound, and by crosslinking in this manner, the initial adhesive force and cohesive force of the film for forming a thermosetting protective film can be adjusted.

Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like.

When an acrylic resin having the above-described functional group is used as the polymer component (A), the composition (III-1) and the film for forming a thermosetting protective film contain a crosslinking agent that reacts with the functional group by heating as a crosslinking agent (F). You can do it. Examples of the crosslinking agent that reacts with the functional group by heating include a block isocyanate compound in which an isocyanate group of an organic polyvalent isocyanate compound is blocked, a polyfunctional compound having transesterification reactivity, and the like.

The composition (III-1) and the crosslinking agent (F) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the case of using a crosslinking agent (F), in the composition (III-1), the content of the crosslinking agent (F) is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the polymer component (A), and 0.1 to 10 It is more preferable that it is a mass part, and it is especially preferable that it is 0.5-5 mass parts. When the content of the crosslinking agent (F) is more than the lower limit, the effect of using the crosslinking agent (F) is more remarkably obtained. Further, when the content of the crosslinking agent (F) is equal to or less than the upper limit, excessive use of the crosslinking agent (F) is suppressed.

[Energy ray curable resin (G)]

The composition (III-1) and the film for forming a thermosetting protective film may contain an energy ray-curable resin (G). Since the film for thermosetting protective film formation contains an energy ray-curable resin (G), the characteristic can be changed by irradiation of an energy ray.

The energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.

Examples of the energy ray-curable compound include a compound having at least one polymerizable double bond in the molecule, and an acrylate compound having a (meth)acryloyl group is preferable.

Examples of the acrylate compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate , Dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) Chain aliphatic skeleton-containing (meth)acrylates such as acrylates; Cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyldi(meth)acrylate; Polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; Oligoester (meth)acrylate; Urethane (meth)acrylate oligomers; Epoxy modified (meth)acrylate; Polyether (meth)acrylate other than the polyalkylene glycol (meth)acrylate; Itaconic acid oligomer, etc. are mentioned.

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said energy ray-curable compound, it is more preferable that it is 300-10000.

The energy ray-curable compound used for polymerization may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The energy ray-curable resin (G) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using an energy ray-curable resin (G), in the composition (III-1), the content ratio of the energy ray-curable resin (G) to the total mass of the composition (III-1) is 1 to 95% by mass. It is preferable, it is more preferable that it is 5 to 90 mass %, and it is especially preferable that it is 10 to 85 mass %.

[Photopolymerization initiator (H)]

When the composition (III-1) and the film for forming a thermosetting protective film contain an energy ray-curable resin (G), in order to efficiently proceed the polymerization reaction of the energy ray-curable resin (G), a photopolymerization initiator (H) is contained, and You may have it.

As the photoinitiator (H) in the composition (III-1), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin Benzoin compounds such as methyl benzoate and benzoin dimethyl ketal; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-1-(4 Acetophenone compounds such as -(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-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-hydroxycyclohexylphenyl ketone; 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 quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

Further, as the photopolymerization initiator (H), for example, a photosensitizer such as an amine may be used.

The photopolymerization initiator (H) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using a photoinitiator (H), in the composition (III-1), the content of the photoinitiator (H) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray curable resin (G). , It is more preferable that it is 1-10 mass parts, and it is especially preferable that it is 2-5 mass parts.

[Universal Additive (J)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range that does not impair the effects of the present invention.

The general-purpose additive (J) may be any known one and may be arbitrarily selected according to the purpose, and is not particularly limited, but preferable ones include, for example, a plasticizer, an antistatic agent, an antioxidant, a gettering agent, an ultraviolet absorber, a tackifier, etc. Can be mentioned.

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

The content of the composition (III-1) and the general-purpose additive (J) in the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[menstruum]

It is preferable that the composition (III-1) further contains a solvent. The composition (III-1) containing a solvent becomes good in handleability.

The solvent is not particularly limited, but preferable examples thereof 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 an amide bond) such as dimethylformamide and N-methylpyrrolidone.

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

As the solvent contained in the composition (III-1), more preferable examples include methyl ethyl ketone, toluene, ethyl acetate, etc., in view of the fact that the components contained in the composition (III-1) can be more uniformly mixed. I can.

The content of the solvent in the composition (III-1) is not particularly limited, and for example, it may be appropriately selected according to the kind of components other than the solvent.

<Method for producing a composition for forming a thermosetting protective film>

A composition for forming a thermosetting protective film, such as composition (III-1), is obtained by blending each component for constituting it.

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

The method of mixing each component at the time of mixing is not particularly limited, and the method of mixing by rotating a stirrer or a stirring blade, etc. Mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

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

◎ Film for forming energy ray-curable protective film

The curing conditions for forming the protective film by energy ray-curing the energy ray-curable protective film-forming film are not particularly limited as long as the curing degree is such that the protective film sufficiently exhibits its function, and the type of the energy ray-curable protective film-forming film You just need to select it appropriately according to.

For example, it is preferable that the illuminance of the energy ray at the time of energy ray curing of the energy ray-curable protective film-forming film is 60 to 320 mW/cm 2. In addition, it is preferable that the amount of light of the energy ray at the time of curing is 100 to 1000 mJ/cm 2.

Examples of the film for forming an energy ray-curable protective film include those containing the energy ray-curable component (a) and a light absorber, and preferably contain the energy ray-curable component (a), a light absorber and a filler.

In the film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, preferably having adhesiveness, and more preferably uncured and having adhesiveness.

<Composition for energy ray-curable protective film formation (IV-1)>

As a preferable composition for forming an energy ray-curable protective film, for example, the composition (IV-1) for forming an energy ray-curable protective film containing the energy ray-curable component (a) and a light absorber (in this specification, simply ``composition ( IV-1)" may be abbreviated).

[Energy ray curable component (a)]

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

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group having a weight average molecular weight of 80000 to 2000000 and a compound (a2) having an energy ray-curable group having a molecular weight of 100 to 800,000. . The polymer (a1) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.

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

As a polymer (a1) having an energy ray-curable group 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 other compounds, a group reacting with the functional group, and energy ray-curable An acrylic resin (a1-1) obtained by reacting an energy ray-curable compound (a12) having an energy ray-curable group such as a double bond is mentioned.

Examples of the functional groups capable of reacting with groups of other compounds include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group obtained by substituting one or two hydrogen atoms of the amino group with a group other than a hydrogen atom), and an epoxy group. . However, in terms of preventing corrosion of circuits such as wafers and chips, the functional group is preferably a group other than a carboxyl group. Among these, it is preferable that the said functional group is a hydroxyl group.

・Acrylic polymer (a11) having a functional group

Examples of the acrylic polymer (a11) having a functional group include those obtained by copolymerization of an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to these monomers, a monomer other than an acrylic monomer ( Non-acrylic monomer) may be copolymerized.

Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may be employed also for the polymerization method.

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 hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate. )(Meth)acrylate hydroxyalkyl such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols having no (meth)acryloyl skeleton), such as vinyl alcohol and allyl alcohol, may be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid and citraconic acid; Anhydrides of the ethylenically unsaturated dicarboxylic acids; (Meth)acrylic acid carboxyalkyl esters, such as 2-carboxyethyl methacrylate, etc. are mentioned.

The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer.

The acrylic monomers constituting the acrylic polymer (a11) and having the functional groups may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

Examples of acrylic monomers having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. )Isobutyl acrylate, (meth)acrylic acid sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate, heptyl (meth) acrylate, (meth) acrylate 2-ethylhexyl, (meth) ) Isooctyl acrylate, (meth) acrylate n-octyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, (meth) acrylate, (meth) acrylate undecyl, (meth) acrylate dodecyl (( Meth) lauryl acrylate), (meth) tridecyl acrylate, (meth) tetradecyl acrylate ((meth) myristyl acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((meth) palmityl acrylate) , (Meth)acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester such as heptadecyl (meth)acrylate and octadecyl (meth)acrylate ((meth) acrylate stearyl) has a chain structure having 1 to 18 carbon atoms. have.

In addition, as an acrylic monomer having no functional group, for example, alkoxyalkyl groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate Containing (meth)acrylic acid ester; (Meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; Non-crosslinkable (meth)acrylamide and derivatives thereof; And (meth)acrylic acid esters having non-crosslinkable tertiary amino groups such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

The acrylic monomers constituting the acrylic polymer (a11) and having no functional group may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; Vinyl acetate; Styrene, etc. are mentioned.

The number of the non-acrylic monomers constituting the acrylic polymer (a11) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof 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 unit 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 within such a 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 determined by the curing of the protective film. It becomes possible to adjust the degree to a preferable range.

The number of the acrylic polymers (a11) constituting the acrylic resin (a1-1) may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (that is, the acrylic resin to the total mass of the film in the film for forming an energy ray-curable protective film The content ratio of (a1-1)) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass.

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 an isocyanate group, an epoxy group, and a carboxy group, and the above It is more preferable to have an isocyanate group as a group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group readily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

The number of the energy ray-curable groups in one molecule of the energy ray-curable compound (a12) is not particularly limited, and may be appropriately selected in consideration of physical properties such as shrinkage required for the target protective film. .

For example, the energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups per molecule, and more preferably has 1 to 3 energy ray-curable groups.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meth-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (Bisacryloyloxymethyl) ethyl isocyanate;

An acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound and hydroxyethyl (meth)acrylate;

And acryloyl monoisocyanate compounds obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate.

Among these, it is preferable that the said energy ray-curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 20 to 120 mol%. It is preferable that it is, and it is more preferable that it is 35-100 mol%, and it is especially preferable that it is 50-100 mol%. When the content ratio is within such a range, the adhesive strength of the cured product of the film for forming an energy ray-curable protective film becomes larger. On the other hand, when the energy ray-curable compound (a12) is a monofunctional compound (having one group per molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is different. In the case of a functional compound (having two or more of the above groups per 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.

Here, the "weight average molecular weight" is as previously described.

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

(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 800,000)

Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group having a molecular weight of 100 to 800,000 include a group containing an energy ray-curable double bond, and preferable examples include a (meth)acryloyl group and a vinyl group. Can be lifted.

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

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

Examples of the acrylate compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylic Rate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxydiee Oxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy) Phenyl]propane, tricyclodecanedimethanoldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonandioldi( 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-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di Bifunctional (meth)acrylates such as (meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane;

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

Polyfunctional (meth)acrylate oligomers, such as a urethane (meth)acrylate oligomer, etc. are mentioned.

Among the compounds (a2), as an epoxy resin having an energy ray-curable group and a phenolic resin having an energy ray-curable group, those described in paragraph 0043 of “JP 2013-194102 A” can be used. Such a resin also corresponds to a resin constituting a thermosetting component described later, but is handled as the compound (a2) in the composition (IV-1).

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said compound (a2), it is more preferable that it is 300-10000.

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

[Polymer (b) not having an energy ray-curable group]

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

The polymer (b) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.

Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as "acrylic polymer (b-1)").

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

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

As the alkyl (meth)acrylate, for example, an acrylic monomer not having the functional group constituting the acrylic polymer (a11) described above (the alkyl group constituting the alkyl ester is a chain structure having 1 to 18 carbon atoms ( The same thing as meth) acrylate alkyl ester etc.) is mentioned.

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

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

(Meth) acrylate cycloalkenyl ester, such as (meth) acrylate dicyclopentenyl ester;

Cycloalkenyloxyalkyl (meth)acrylates, such as dicyclopentenyloxyethyl (meth)acrylate, etc. are mentioned.

Examples of the glycidyl group-containing (meth)acrylic acid ester include glycidyl (meth)acrylate.

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

Examples of the substituted amino group-containing (meth)acrylic acid ester include N-methylaminoethyl (meth)acrylate.

Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; Vinyl acetate; Styrene, etc. are mentioned.

The polymer (b) which does not have the energy ray-curable group at least partially cross-linked with a cross-linking agent includes, for example, a reactive functional group in the polymer (b) reacted with a cross-linking agent.

The reactive functional group may be appropriately selected depending on the type of crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent 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. Further, when the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among them, a carboxyl group having high reactivity with an epoxy group is preferable. However, in terms of preventing corrosion of the circuit of the wafer or chip, the reactive functional group is preferably a group other than a carboxyl group.

Examples of the polymer (b) having no energy ray-curable group having a reactive functional group include those obtained by polymerizing at least a monomer having the reactive functional group. In the case of the acrylic polymer (b-1), one having the above reactive functional group may be used as either or both of the above acrylic monomer and non-acrylic monomer as a monomer constituting it. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester. In addition, in the above acrylic monomer or non-acrylic monomer, one or two What is obtained by polymerizing a monomer obtained by substituting at least two hydrogen atoms with the above reactive functional groups is mentioned.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the constituent unit derived from the monomer having the reactive functional group to the total amount of the constituent units constituting it is preferably 1 to 20% by mass, It is more preferable that it is 2-10 mass %. When the ratio is within such a range, in the polymer (b), the degree of crosslinking becomes a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) not having an energy ray-curable group is preferably 10000 to 2000000, more preferably 100000 to 150,000, from the viewpoint of better film-forming properties of the composition (IV-1). . Here, the "weight average molecular weight" is as previously described.

The composition (IV-1) and the energy ray-curable protective film-forming film contain only one type of polymer (b), which does not have an energy ray-curable group, and may be two or more types, and in the case of two or more types, combinations and ratios thereof Can be arbitrarily selected.

Examples of the composition (IV-1) include those containing either or both of the polymer (a1) and the compound (a2). In addition, when the composition (IV-1) 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, further containing the above (a1) It is also desirable. Further, the composition (IV-1) does not contain the compound (a2), and may contain the polymer (a1) and the polymer (b) having no energy ray-curable group together.

When the composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) not having an energy ray-curable group, in the composition (IV-1), the content of the compound (a2) Silver is preferably 10 to 400 parts by mass, and more preferably 30 to 350 parts by mass, based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group to the total content of components other than the solvent (that is, for forming an energy ray-curable protective film 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 mass of the film in the film) is preferably 5 to 90% by mass, and 10 to 80 It is more preferable that it is mass %, and it is especially preferable that it is 20-70 mass %. When the ratio of the content of the energy ray-curable component is within such a range, the energy ray-curable property of the film for forming an energy ray-curable protective film becomes better.

[Light absorber]

The light absorbing agent is a component that absorbs light while it is present in the protective film, thereby facilitating a rise in temperature of the protective film.

When the composition (IV-1) and the film for forming an energy ray-curable protective film contain a light absorbing agent, the X _max of the protective film becomes larger, and it becomes easier to _{increase Z 150} and Z _200.

The light absorbing agent contained in the composition (IV-1) and the film for forming an energy ray-curable protective film is the same as the light absorbing agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film described above.

The aspect of containing the light absorber in the composition (IV-1) and the film for forming an energy ray-curable protective film may be the same as the aspect of containing the light absorber (I) in the composition (III-1) and the film for forming a thermosetting protective film.

For example, it is preferable that the light absorbing agent contained in the composition (IV-1) and the film for forming an energy ray-curable protective film can absorb either or both of visible light and infrared light.

The light absorbers contained in the composition (IV-1) and the energy ray-curable protective film-forming film may have only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. For example, the composition (IV-1) and the film for forming an energy ray-curable protective film may contain only one or two or more types of organic pigments as a light absorbing agent, and may contain only one or two or more types of inorganic pigments, You may contain organic pigment|dye and inorganic pigment together 1 type or 2 or more types.

The composition (IV-1) and the film for forming an energy ray-curable protective film preferably contain two or more types of light absorbers capable of absorbing either or both of visible light and infrared light, and more preferably contain 2 to 7 types.

When the composition (IV-1) and the film for forming an energy ray-curable protective film contain an inorganic pigment as a light absorbing agent, it is preferable to contain a carbon material, and more preferably, a carbon material and an organic dye are included together.

In the composition (IV-1), the ratio of the content of the light absorber to the total content of all components other than the solvent (i.e., light to the total mass of the film for forming an energy ray-curable protective film in the film for forming an energy ray-curable protective film. The content ratio of the water absorbing agent) may be 0.1 to 20% by mass. When the ratio is greater than or equal to the lower limit, the effect of using a light absorbing agent is more remarkably obtained. When the ratio is equal to or less than the upper limit, excessive use of the light absorbing agent is suppressed.

The composition (IV-1) and the film for forming an energy ray-curable protective film are, depending on the purpose, the energy ray-curable component (a), the polymer (b), and a thermosetting component, filler, which does not correspond to any of the light absorbing agent, It may contain 1 type or 2 or more types selected from the group consisting of a coupling agent, a crosslinking agent, a photoinitiator, and a general-purpose additive.

As the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, and general-purpose additive in the composition (IV-1), the thermosetting component (B), the filler (D), and the couple in the composition (III-1), respectively. The same things as ring agent (E), crosslinking agent (F), photoinitiator (H), and general-purpose additive (J) are mentioned.

For example, when the composition (IV-1) contains a thermosetting component, the film for forming an energy ray-curable protective film formed by using the composition (IV-1) improves adhesion to an adherend by heating, The strength of the protective film formed from this energy ray-curable protective film-forming film is also improved.

In the composition (IV-1), the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, and general-purpose additive may each be used alone or in combination of two or more, or two or more. When used in combination, combinations and ratios thereof can be arbitrarily selected.

The content of the thermosetting component, filler, coupling agent, crosslinking agent, photoinitiator, and general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

The composition (IV-1) preferably further contains a solvent from the viewpoint of improving its handling properties by dilution.

The solvent contained in the composition (IV-1) includes, for example, the same solvent as the solvent in the composition (III-1).

The number of solvents contained in the composition (IV-1) may be one or two or more.

The content of the solvent in the composition (IV-1) is not particularly limited, and for example, it may be appropriately selected according to the kind of components other than the solvent.

<Method of manufacturing composition for energy ray-curable protective film formation>

A composition for forming an energy ray-curable protective film such as composition (IV-1) is obtained by blending each component for constituting it.

The composition for forming an energy ray-curable protective film can be prepared in the same manner as in the case of the composition for forming a thermosetting protective film described above, except that, for example, the types of the compounding components are different.

◎ Film for forming a non-curable protective film

Preferred films for forming a non-curable protective film include, for example, those containing a thermoplastic resin, a light absorber, and a filler.

<Composition for forming a non-curable protective film (V-1)>

As a preferable composition for forming a non-curable protective film, for example, the composition for forming a non-curable protective film (V-1) containing the thermoplastic resin, a light absorber, and a filler (in this specification, simply ``composition (V-1) It may be abbreviated as "), etc. are mentioned.

[Thermoplastic resin]

The thermoplastic resin is not particularly limited.

As the thermoplastic resin, more specifically, for example, curing properties of acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. as contained components of the above-described composition (III-1) The same thing as resin other than that is mentioned.

The thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the composition (V-1), the ratio of the content of the thermoplastic resin to the total content of components other than the solvent (that is, the thermoplastic resin relative to the total mass of the film for forming a non-curable protective film in the film for forming a non-curable protective film The content ratio of) is preferably 25 to 75% by mass.

[Light absorber]

The light absorbing agent is a component that absorbs light while it is present in the protective film, thereby facilitating a rise in temperature of the protective film.

When the composition (V-1) and the film for forming a non-curable protective film contain a light absorbing agent, the X _max of the protective film becomes larger, and it becomes easier to _{increase Z 150} and Z _200.

The light absorbing agent contained in the composition (V-1) and the film for forming a non-curable protective film is the same as the light absorbing agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film described above.

The aspect of containing the light absorber in the composition (V-1) and the film for forming a non-curable protective film may be the same as the aspect of containing the light absorber (I) in the composition (III-1) and the film for forming a thermosetting protective film.

For example, the light absorbing agent contained in the composition (V-1) and the film for forming a non-curable protective film is preferably capable of absorbing either or both of visible light and infrared light.

The light absorbing agent contained in the composition (V-1) and the film for forming a non-curable protective film may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. For example, the composition (V-1) and the film for forming a non-curable protective film may contain only one or two or more types of organic pigments as a light absorbing agent, and may contain only one or two or more types of inorganic pigments. You may contain 1 type or 2 or more types together of a pigment|dye and an inorganic pigment.

The composition (V-1) and the film for forming a non-curable protective film preferably contain two or more types of light absorbers capable of absorbing either or both of visible light and infrared light, and more preferably contain 2 to 7 types.

When the composition (V-1) and the film for forming a non-curable protective film contain an inorganic pigment as a light absorbing agent, it is preferable to contain a carbon material, and more preferably, a carbon material and an organic dye are included together.

In the composition (V-1), the ratio of the content of the light absorber to the total content of all components other than the solvent (that is, of the light absorbing agent to the total mass of the film for forming a non-curable protective film in the film for forming a non-curable protective film) The content ratio) may be 0.1 to 20% by mass. When the ratio is greater than or equal to the lower limit, the effect of using a light absorbing agent is more remarkably obtained. When the ratio is equal to or less than the upper limit, excessive use of the light absorbing agent is suppressed.

[filling]

The film for forming a non-curable protective film containing a filler exhibits the same effects as the film for forming a thermosetting protective film containing the filler (D).

Examples of the filler contained in the composition (V-1) and the film for forming a non-curable protective film include the same fillers as the filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film.

The number of fillers contained in the composition (V-1) and the film for forming a non-curable protective film may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the composition (V-1), the ratio of the content of the filler to the total content of all components other than the solvent (that is, the ratio of the content of the filler to the total mass of the film for forming a non-curable protective film in the film for forming a non-curable protective film ) Is preferably 25 to 75% by mass. When the ratio is within such a range, it becomes easier to adjust the thermal expansion coefficient of the film for forming a non-curable protective film (that is, the protective film) as in the case of using the composition (III-1).

The composition (V-1) may contain other components that do not correspond to any of the thermoplastic resin, the light absorber, and the filler according to the purpose.

The other components are not particularly limited and may be arbitrarily selected according to the purpose.

In the composition (V-1), the other components may be used singly or in combination of two or more, and when two or more are used in combination, combinations and ratios thereof can be arbitrarily selected.

The content of the other components of the composition (V-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

The composition (V-1) preferably further contains a solvent from the viewpoint of improving its handling properties by dilution.

Examples of the solvent contained in the composition (V-1) include the same solvents as those in the above-described composition (III-1).

The number of solvents contained in the composition (V-1) may be one or two or more.

The content of the solvent in the composition (V-1) is not particularly limited, and for example, it may be appropriately selected according to the kind of components other than the solvent.

<Method of producing a composition for forming a non-curable protective film>

A composition for forming a non-curable protective film such as composition (V-1) is obtained by blending each component for constituting it.

The composition for forming a non-curable protective film can be prepared in the same manner as in the case of the composition for forming a thermosetting protective film described above, except that, for example, the types of the compounding components are different.

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

The film 13 for protective film formation shown here is provided with the 1st peeling film 151 on the one side (in this specification, it may be called "the 1st surface") 13a, and said 1st The second release film 152 is provided on the other surface (in this specification, it may be referred to as a "second surface") 13b on the opposite side to the surface 13a.

Such a protective film-forming film 13 is preferably stored in a roll shape, for example.

The protective film-forming film 13 has the above-described characteristics.

The protective film-forming film 13 may be formed using the above-described protective film-forming composition.

Both the first release film 151 and the second release film 152 may be known. The first release film 151 and the second release film 152 may be the same as each other, for example, may be different from each other, for example, the peeling force required when peeling from the film-like adhesive 13 is different from each other. .

In the film 13 for forming a protective film shown in FIG. 1, the exposed surface formed by removal of either of the first release film 151 and the second release film 152 becomes an affixed surface to the back surface of a wafer (not shown). . In addition, the exposed surface resulting from the removal of the other side of the first release film 151 and the second release film 152 is a support sheet or dicing sheet (referred to as a ``dicing tape'' in this specification). It becomes the affixed surface of (I do). For example, in the case where the first surface 13a is an affixed surface to the back surface of the wafer, the second surface 13b becomes the affixing surface of a support sheet or a dicing sheet.

In Fig. 1, an example in which a release film is formed on both surfaces (first side 13a, second side 13b) of the film 13 for forming a protective film is shown, but the release film is a film 13 for forming a protective film. ), that is, only the first surface 13a or only the second surface 13b may be formed.

The film for protective film formation of this embodiment can be affixed to the back surface of a wafer, without being used together with the support sheet mentioned later. In that case, a release film may be formed on the surface of the film for protective film formation opposite to the surface affixed to the wafer, and this release film may be removed at an appropriate timing. A dicing sheet is affixed to the exposed surface of the film for protective film formation after removing the release film, and dicing, that is, dividing the wafer and cutting the film or protective film for forming a protective film, can produce a chip with a protective film. .

On the other hand, by using the film for protective film formation of this embodiment together with the support sheet mentioned later, it is possible to construct the composite sheet for protective film formation which can perform both formation of a protective film and dicing. Hereinafter, such a composite sheet for forming a protective film will be described.

◇Composite sheet for forming a protective film

The composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet and a film for forming a protective film formed on one side of the support sheet, and the film for forming a protective film is an embodiment of the present invention described above. It is a film for forming a protective film according to its shape.

Since the protective film-forming composite sheet of the present embodiment is provided with the protective film-forming film, the electrical connection strength between the protruding electrode and the connection pad on the circuit board as a chip on which the protective film is formed is measured in the manufacturing process of the substrate device. , Can be made stronger.

In this specification, even after the protective film-forming film is cured, this laminated structure is referred to as a "protective film-forming composite sheet" as long as the laminated structure of the cured product of the support sheet and the protective film-forming film is maintained.

Hereinafter, each layer constituting 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 a plurality of layers of two or more layers. When the supporting sheet is made of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited unless the effect of the present invention is impaired.

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

For example, when the film for forming a protective film has energy ray curability, it is preferable that the supporting sheet transmit energy rays.

The supporting sheet includes, for example, a base material and an adhesive layer formed on one side of the base material; What consists only of a base material, etc. are mentioned. When the support sheet is provided with the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is disposed between the substrate and the protective film-forming film in the protective film-forming composite sheet.

When a support sheet provided with a substrate and an adhesive layer is used, in the composite sheet for forming a protective film, the adhesive force or adhesion between the support sheet and the film for forming a protective film can be easily adjusted.

When a supporting sheet composed of only a base material is used, a composite sheet for forming a protective film can be manufactured at low cost.

An example of the composite sheet for forming a protective film of the present embodiment will be described below for each type of such support sheet with reference to the drawings.

2 is a cross-sectional view schematically showing an example of 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 reference numerals as those in the illustrated drawings are assigned to the same constituent elements as those shown in the previously described drawings, and detailed descriptions thereof will be omitted.

The protective film-forming composite sheet 101 shown here is formed on the support sheet 10 and one side of the support sheet 10 (in this specification, it may be referred to as ``first surface'') 10a. It is comprised with the film 13 for protective film formation.

The support sheet 10 includes a base 11 and an adhesive layer 12 formed on one side (ie, the first side) 11a of the base 11. Among the composite sheet 101 for forming a protective film, the pressure-sensitive adhesive layer 12 is disposed between the substrate 11 and the film 13 for forming a protective film.

That is, the protective film-forming composite sheet 101 is constituted by laminating the base material 11, the pressure-sensitive adhesive layer 12, and the protective film-forming film 13 in this order in their thickness direction.

The surface of the supporting sheet 10 on the side of the film 13 for forming a protective film (in this specification, it may be referred to as a ``first surface'') 10a is different from the side of the substrate 11 of the pressure-sensitive adhesive layer 12 It is the same as 12a on the opposite side (in this specification, it may be referred to as "the first surface").

The protective film-forming composite sheet 101 further includes a jig adhesive layer 16 and a release film 15 on the protective film-forming film 13.

In the protective film-forming composite sheet 101, the protective film-forming film 13 is laminated on the entire surface or almost the entire surface of the first surface 12a of the pressure-sensitive adhesive layer 12, and the protective film-forming film 13 A jig adhesive layer 16 is laminated on a part of 13a on the side opposite to the side of the pressure-sensitive adhesive layer 12 (in this specification, it may be referred to as the ``first surface''), that is, in the area near the periphery, have. In addition, of the first surface 13a of the protective film forming film 13, a region in which the jig adhesive layer 16 is not laminated, and the protective film forming film 13 side of the jig adhesive layer 16 The release film 15 is laminated on the opposite side surface (in this specification, it may be referred to as "first surface") 16a.

It is not limited to the case of the composite sheet 101 for protective film formation, In the composite sheet for protective film formation of this embodiment, the release film (for example, the release film 15 shown in FIG. 1) has an arbitrary structure, The composite sheet for forming a protective film of the present embodiment may or may not be equipped with a release film.

In the composite sheet 101 for forming a protective film, a partial gap may be formed between the release film 15 and the layer in direct contact with the release film 15.

For example, here, the state in which the release film 15 is in contact (lamination) on the side surface 16c of the jig adhesive layer 16 is shown, but the release film 15 is in contact with the side surface 16c. In some cases, it is not. In addition, here, the state in which the release film 15 is in contact (lamination) in a region near the jig adhesive layer 16 of the first surface 13a of the protective film forming film 13 is shown, but the above region In some cases, the release film 15 is not in contact with each other.

In addition, the boundary between the first surface 16a and the side surface 16c of the jig adhesive layer 16 may not be clearly distinguishable in some cases.

The above point is the same also in the composite sheet for forming a protective film according to another embodiment provided with an adhesive layer for a jig.

The jig adhesive layer 16 is used to fix the protective film-forming composite sheet 101 to a jig such as a ring frame.

The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or may have a multilayer structure in which layers containing an adhesive component are laminated on both surfaces of a sheet serving as a core material.

In the protective film obtained from the composite sheet 101 for forming a protective film, as described above, Z ₁₅₀ is 0.38 or more, and Z ₂₀₀ is 0.33 or more.

In the protective film forming composite sheet 101, the back surface of the wafer is affixed to the first surface 13a of the protective film forming film 13 in the state where the release film 15 is removed, and the jig adhesive layer 16 The first surface (16a) of is used by being affixed to a jig such as a ring frame.

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

The protective film-forming composite sheet 102 shown here has different shapes and sizes of the protective film-forming film, and the jig adhesive layer is laminated on the first side of the pressure-sensitive adhesive layer, not the first side of the protective film-forming film. It is the same as the composite sheet 101 for forming a protective film shown in Fig. 1 except that there is a point.

More specifically, in the protective film-forming composite sheet 102, the protective film-forming film 23 is a partial region of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the width of the pressure-sensitive adhesive layer 12 It is laminated in a region on the center side in the direction (left and right directions in Fig. 3). Further, of the first surface 12a of the pressure-sensitive adhesive layer 12, the jig adhesive layer 16 is laminated in a region in which the protective film-forming film 23 is not laminated, that is, a region in the vicinity of the periphery. In addition, the surface of the protective film-forming film 23 on the opposite side to the adhesive layer 12 side (in this specification, it may be referred to as the ``first surface'') 23a and the jig adhesive layer 16 The release film 15 is laminated on the first surface 16a.

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

The protective film-forming composite sheet 103 shown here is the same as the protective film-forming composite sheet 102 shown in FIG. 3 except that the jig adhesive layer 16 is not provided.

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

The protective film-forming composite sheet 104 shown here is the same as the protective film-forming composite sheet 101 shown in FIG. 2 except that the support sheet 20 is provided instead of the support sheet 10.

The support sheet 20 is made of only the substrate 11.

That is, the protective film-forming composite sheet 104 is constituted by laminating the substrate 11 and the protective film-forming film 13 in the thickness direction thereof.

The surface of the support sheet 20 on the side of the film 13 for forming a protective film (in this specification, it may be referred to as a ``first surface'') 20a is the same as the first surface 11a of the substrate 11 Do.

The substrate 11 has adhesiveness at least on its first surface 11a.

The composite sheet for forming a protective film of the present embodiment is not limited to those shown in Figs. 1 to 5, and within a range that does not impair the effects of the present invention, some configurations of those shown in Figs. 1 to 5 have been changed or deleted. It may be that another configuration has been added to the one described so far. More specifically, it is as follows.

Up to this point, only the composite sheet for forming a protective film 104 shown in Fig. 5 is shown for the composite sheet for forming a protective film having a support sheet composed of only a substrate, but the composite sheet for forming a protective film provided with a support sheet composed of only a substrate is an example. For example, in the composite sheet 102 for forming a protective film shown in Fig. 3 or the composite sheet 103 for forming a protective film shown in Fig. 4, those not provided with the pressure-sensitive adhesive layer 12 may be mentioned. However, this is an example of another composite sheet for forming a protective film provided with a support sheet made of only a base material.

Up to this point, only the composite sheet for protective film formation 103 shown in Fig. 4 is shown for the composite sheet for forming a protective film that does not have a jig adhesive layer, but it is a composite sheet for forming a protective film that does not have a jig adhesive layer. For example, in the composite sheet 101 for forming a protective film shown in Fig. 2, the jig adhesive layer 16 is not provided; In the composite sheet 104 for forming a protective film shown in FIG. 5, the thing which does not have the adhesive layer 16 for a jig is mentioned. However, this is an example of another composite sheet for forming a protective film that does not have a jig adhesive layer.

Up to this point, as the layers constituting the composite sheet for forming a protective film, a substrate, an adhesive layer, a film for forming a protective film, and a release film have been shown. do.

The type of the other layer is not particularly limited, and may be arbitrarily selected according to the purpose.

The arrangement position, shape, size, etc. of the other layers may also be arbitrarily selected according to the type, and are not particularly limited.

As the other layer, for example, it is disposed between the supporting sheet and the protective film forming film to control the peelability of the protective film forming film or the cured product from the supporting sheet. An intermediate layer and the like.

However, this is an example of another composite sheet for forming a protective film provided with the other layer.

In the composite sheet for forming a protective film of the present embodiment, the size and shape of each layer can be arbitrarily selected according to the purpose.

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

○ Description

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

Examples of the resin include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; Ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer (copolymers obtained using ethylene as a monomer); Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer (resins 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 wholly aromatic polyesters in which all structural units have an aromatic cyclic group; A copolymer of two or more of the above polyesters; Poly(meth)acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone; Polyether ketone, etc. are mentioned.

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

In addition, as the resin, for example, a crosslinked resin obtained by crosslinking one or two or more of the resins exemplified so far; Modified resins such as ionomers using one or two or more of the resins exemplified so far can also be mentioned.

The number of resins constituting the substrate may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

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

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

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

The substrate may be transparent or opaque, may be colored depending on the purpose, or may be deposited with another layer.

For example, when the film for forming a protective film has energy ray curing properties, it is preferable that the substrate transmits energy rays.

In order to adjust the adhesion with the layer formed thereon (for example, a pressure-sensitive adhesive layer, a film for forming a protective film, or the other layer), the substrate may be subjected to uneven treatment by sand blasting or solvent treatment; Oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet radiation treatment, flame treatment, chromic acid treatment, and hot air treatment; Lipophilic treatment; Hydrophilic treatment or the like may be applied to the surface. In addition, the surface of the substrate may be subjected to a primer treatment.

The substrate may have adhesiveness on at least one side by containing a component in a specific range (eg, resin, etc.).

The substrate can be prepared by a known method. For example, the base material containing a resin can be manufactured by molding the resin composition containing the said 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 adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin.

In this specification, both a resin having adhesiveness and a resin having adhesiveness are contained in the "adhesive resin". For example, in the adhesive resin, not only the resin itself has adhesiveness, but also a resin that exhibits adhesiveness when used in combination with other components such as additives, or a resin that exhibits adhesiveness by the presence of a trigger such as heat or water. Included.

The pressure-sensitive adhesive layer may consist of one layer (single layer), may consist of 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 the plurality of layers is specifically limited. It doesn't work.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but it 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 thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer consisting of a plurality of layers means the total thickness of all the layers constituting the pressure-sensitive adhesive layer.

The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. That is, the pressure-sensitive adhesive layer may be either energy ray-curable or non-energy ray-curable. The energy ray-curable pressure-sensitive adhesive layer can easily adjust physical properties before and after curing.

The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying as necessary, the pressure-sensitive adhesive layer can be formed on a target site. The content ratio between components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the content ratio between the components in the pressure-sensitive adhesive layer.

Coating of the pressure-sensitive adhesive composition can be performed, for example, in the same manner as in the case of coating the composition for forming a protective film described above.

In the case of forming the pressure-sensitive adhesive layer on the substrate, for example, the pressure-sensitive adhesive composition may be coated on the substrate and dried as necessary to laminate the pressure-sensitive adhesive layer on the substrate. In addition, in the case of forming an adhesive layer on a substrate, for example, by coating an adhesive composition on a release film and drying as necessary to form a pressure-sensitive adhesive layer on the release film, the exposed surface of the pressure-sensitive adhesive layer is described as a substrate. By bonding with one surface of, an adhesive layer may be laminated on the substrate. In this case, the release film may be removed at any timing during the manufacturing process or the use process of the composite sheet for forming a protective film.

The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, regardless of whether the pressure-sensitive adhesive layer is energy ray-curable or non-energy-ray-curable. However, when the adhesive composition contains the solvent mentioned later, it is preferable to heat-dry. And the pressure-sensitive adhesive composition containing a solvent is preferably heated and dried at 70 to 130°C for 10 seconds to 5 minutes, for example.

When the pressure-sensitive adhesive layer is energy-ray-curable, the energy-ray-curable pressure-sensitive adhesive composition is, for example, a non-energy-ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”). And, the pressure-sensitive adhesive composition (I-1) containing an energy ray-curable compound; Containing an 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); The adhesive resin (I-2a) and the pressure-sensitive adhesive composition (I-3) containing an energy ray-curable compound can be mentioned.

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

[Adhesive resin (I-1a)]

The pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), the pressure-sensitive adhesive composition (I-3), and the pressure-sensitive adhesive composition (I-4) (hereinafter, encompassing these pressure-sensitive adhesive compositions, ``Adhesive composition (I-1) ) To (I-4)"), the adhesive resin (I-1a) is preferably an acrylic resin.

Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

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

It is preferable that the said acrylic polymer further has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylate alkyl ester.

As the functional group-containing monomer, for example, the functional group becomes a starting point for crosslinking by reacting with a crosslinking agent described later, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later, thereby introducing an unsaturated group into the side chain of the acrylic polymer. What makes it possible is mentioned.

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

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

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

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

In the pressure-sensitive adhesive compositions (I-1) to (I-4), the constitutional units of the acrylic resin such as the acrylic polymer may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof Can be arbitrarily selected.

In the above acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass with respect to the total amount of the structural unit.

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

In the pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4), the content ratio of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4) is 5 It is preferable that it is -99 mass %.

[Adhesive resin (I-2a)]

The pressure-sensitive adhesive resin (I-2a) in the pressure-sensitive adhesive compositions (I-2) and (I-3) contains, for example, an unsaturated group having an energy ray-polymerizable unsaturated group in the functional group in the pressure-sensitive adhesive resin (I-1a). It is obtained by reacting a compound.

The unsaturated group-containing compound is a compound having a group capable of bonding to 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 a (meth)acryloyl group, a vinyl group (ethenyl group), and an allyl group (2-propenyl group), and a (meth)acryloyl group is preferable.

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

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) or (I-3) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. have.

In the adhesive composition (I-2) or (I-3), the content ratio of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-2) or (I-3) is 5 to 99% by mass It is preferable to be.

[Energy ray curable compound]

Examples of the energy ray-curable compound in the pressure-sensitive adhesive compositions (I-1) and (I-3) include a monomer or oligomer that has an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays.

Among the energy ray-curable compounds, monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth) Polyhydric (meth)acrylates such as acrylate, 1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol (meth)acrylate; Urethane (meth)acrylate; Polyester (meth)acrylate; Polyether (meth)acrylate; Epoxy (meth)acrylate, etc. are mentioned.

Among the energy ray-curable compounds, oligomers include, for example, oligomers obtained by polymerization of the monomers exemplified above.

The energy ray-curable compounds contained in the pressure-sensitive adhesive composition (I-1) or (I-3) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content ratio of the energy ray-curable compound to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95% by mass. 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 with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a).

[Crosslinking agent]

When using the above acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a), the adhesive composition (I-1) or (I- It is preferable that 4) further contains a crosslinking agent.

In addition, in the case of using the acrylic polymer having structural units derived from the same functional group-containing monomer as in the adhesive resin (I-1a), for example, as the adhesive resin (I-2a), the adhesive composition (I-2) Alternatively, (I-3) may further contain a crosslinking agent.

The crosslinking agent reacts with the functional group, for example, to crosslink the adhesive resins (I-1a) or the adhesive resins (I-2a).

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

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1), (I-2) or (I-4) may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. .

In the pressure-sensitive adhesive composition (I-1) or (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a).

In the pressure-sensitive adhesive composition (I-2) or (I-3), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a).

[Photopolymerization initiator]

The pressure-sensitive adhesive compositions (I-1), (I-2), and (I-3) (hereinafter, these pressure-sensitive adhesive compositions are encompassed and abbreviated as “adhesive compositions (I-1) to (I-3)”) are And may further contain a photoinitiator. Even if the pressure-sensitive adhesive compositions (I-1) to (I-3) containing a photoinitiator are irradiated with relatively low energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin 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-hydroxycyclohexylphenyl ketone; 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 quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

Further, as the photopolymerization initiator, for example, a photosensitizer such as amine may be used.

The photopolymerization initiators contained in the pressure-sensitive adhesive compositions (I-1) to (I-3) may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the photoinitiator is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the energy ray-curable compound.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a).

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

[Other additives]

The pressure-sensitive adhesive compositions (I-1) to (I-4) 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 above other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, coloring agents (pigments, dyes), sensitizers, tackifiers, reaction retardants, and crosslinking accelerators (catalysts ), and other known additives.

On the other hand, the reaction retarder means, for example, by the action of a catalyst incorporated in the pressure-sensitive adhesive compositions (I-1) to (I-4), to the pressure-sensitive adhesive compositions (I-1) to (I-4) during storage. WHEREIN: It is a component which suppresses progress of the crosslinking reaction which is not intended. Examples of the reaction retarding agent include forming a chelate complex by chelate to a catalyst, and more specifically, one having two or more carbonyl groups (-C(=O)-) in one molecule. .

The other additives contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The content of the other additives in the pressure-sensitive adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately selected according to the kind.

[menstruum]

The pressure-sensitive adhesive compositions (I-1) to (I-4) may contain a solvent. When the pressure-sensitive adhesive compositions (I-1) to (I-4) contain a solvent, the application aptitude to the surface to be coated is improved.

The solvent is preferably an organic solvent. 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; Alcohol, such as 1-propanol and 2-propanol, etc. are mentioned.

The number of solvents contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The content of the solvent in the pressure-sensitive adhesive compositions (I-1) to (I-4) is not particularly limited and may be appropriately adjusted.

○ Manufacturing method of adhesive composition

The pressure-sensitive adhesive compositions such as pressure-sensitive adhesive compositions (I-1) to (I-4) are obtained by blending the pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition such as components other than the pressure-sensitive adhesive.

The pressure-sensitive adhesive composition can be produced by the same method as in the case of the composition for forming a thermosetting protective film described above, except that, for example, the types of the blending components are different.

Another example of the film for forming a protective film of the present embodiment is a film for forming a protective film for forming a protective film on the back surface of the chip, the maximum value (X _max ) of the absorbance at a wavelength of 1400 to 1500 nm of the protective film, and _{Using the specific heat (S 150} ) at 150° C. of the protective film, the formula:

Z ₁₅₀ ＝X _max ／S ₁₅₀

_{Z 150} calculated by is 0.38 or more, and using the X _{max and the specific heat (S 200} ) at 200° C. of the protective film, the formula:

Z ₂₀₀ ＝X _max ／S ₂₀₀

_{Z 200} calculated by is 0.33 or more, the film for forming a protective film contains a polymer component, a thermosetting component, and a light absorber, the polymer component is an acrylic resin, the thermosetting component is an epoxy-based thermosetting resin, and the light The absorbent is one or two or more selected from the group consisting of organic pigments and inorganic pigments, and the content ratio of the polymer component to the total mass of the protective film-forming film in the protective film-forming film is 5 to 80 mass. %, with respect to 100 parts by mass of the content of the polymer component in the protective film-forming film, the content ratio of the thermosetting component is 10 to 200 parts by mass, and the protective film-forming film in the protective film-forming film The ratio of the content of the light absorbing agent to the total mass is 0.1 to 20% by mass.

◇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 above-described layers so as to have a corresponding positional relationship, and adjusting the shape of some or all of the layers as necessary. The method of forming each layer is as described above.

For example, when manufacturing a support sheet, in the case of laminating an adhesive layer on a substrate, the above-described adhesive composition may be coated on the substrate and dried as necessary.

In addition, by coating the pressure-sensitive adhesive composition on the release film and drying as necessary, a pressure-sensitive adhesive layer is formed on the release film, and the exposed surface of the pressure-sensitive adhesive layer is bonded to one surface of the substrate. Layers can be stacked. At this time, it is preferable to apply the pressure-sensitive adhesive composition to the peeling-treated surface of the peeling film.

Up to this point, the case of laminating the pressure-sensitive adhesive layer on the substrate has been exemplified, but the above-described method can also be applied, for example, in the case of laminating an intermediate layer or the other layer on the substrate.

On the other hand, for example, when a protective film-forming film is additionally laminated on the pressure-sensitive adhesive layer laminated on the substrate, it is possible to directly form the protective film-forming film by coating the protective film-forming composition on the pressure-sensitive adhesive layer. . 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 the composition for forming this layer. In this way, a new layer (hereinafter, abbreviated as the ``second layer'') is formed on any one layer (hereinafter abbreviated as the ``first layer'') stacked on the substrate, and two consecutive layers are stacked. In the case of forming a structure (that is, a laminated structure of a first layer and a second layer), a method of coating a composition for forming the second layer on the first layer and drying as necessary may be applied. I can.

However, the second layer is formed in advance on the release film using the composition for forming it, and the exposed surface of the formed second layer opposite to the side in contact with the release film is separated from the exposed surface of the first layer. It is preferable to form a continuous two-layer laminated structure by bonding. At this time, it is preferable to apply the composition to the peeling-treated surface of the peeling film. The release film may be removed as necessary after formation of the laminated structure.

Here, the case of laminating a protective film-forming film on the pressure-sensitive adhesive layer has been exemplified, but the target laminated structure may be arbitrarily selected, such as, for example, a case of laminating an intermediate layer or the other layer on the pressure-sensitive adhesive layer.

In this way, all layers other than the base material constituting the composite sheet for forming a protective film can be formed in advance on the release film and laminated by a method of bonding them to the surface of the target layer. Therefore, such a process is employed as necessary. The layer to be formed may be appropriately selected to produce a protective film-forming composite sheet.

On the other hand, the composite sheet for forming a protective film is usually stored in a state in which a release film is adhered to the surface of the outermost layer (for example, a film for forming a protective film) on the opposite side of the supporting sheet. Therefore, a composition for forming a layer constituting an outermost layer, such as a composition for forming a protective film, is applied on this release film (preferably, the peeling treatment surface thereof) and, if necessary, dried to form the outermost layer on the release film. A layer constituting the layer is formed, and the remaining layers are laminated on the exposed side opposite to the side in contact with the release film of this layer by any one of the above-described methods, and are bonded without removing the release film. By keeping it, a composite sheet for forming a protective film on which a release film was formed is obtained.

◇Method of manufacturing a chip with a protective film (how to use a film for forming a protective film and a composite sheet for forming a protective film)

The protective film-forming film and the protective film-forming composite sheet may be used to manufacture a chip on which the protective film is formed.

<<production method 1>>

As a method of manufacturing a chip on which the protective film is formed by attaching the film for forming a protective film to a wafer without using the film for forming a protective film in combination with a support sheet, for example,

A laminate (1) comprising a wafer and a film for forming a protective film formed on the back surface of the wafer, or a wafer and a protective film formed on the back surface of the wafer through a process of attaching a protective film forming film to the back surface of the wafer. A first lamination step of obtaining the equipped laminate 1 ′, and

A dicing sheet is placed on the side opposite to the wafer side of the protective film-forming film in the laminate (1), or on the side opposite to the wafer side of the protective film in the laminate (1'). Through a process of affixing, the dicing sheet, the film for forming a protective film, and the wafer are laminated in this order in their thickness direction to form a laminate (2), or the dicing sheet, and the A second lamination step for obtaining a layered product 2'configured by laminating a protective film and the wafer in this order in their thickness direction; and

After dividing the wafer in the laminate 2 to produce a chip, and through a process of cutting the protective film forming film according to the divided portions of the wafer, the chip and the cut protective film formed on the back surface of the chip To obtain a chip assembly with a protective film forming film formed by holding a plurality of protective film forming films with a forming film on the dicing sheet, or dividing the wafer in the laminate (2') The dicing sheet is formed with a chip having a plurality of protective films including the chip and the cut protective film formed on the back surface of the chip through a process of manufacturing a chip and cutting the protective film according to the divided portions of the wafer. A dividing/cutting process to obtain a chip assembly with a protective film formed by being held on the phase, and

The chip on which the protective film is formed in the chip assembly on which the protective film-forming film is formed, or the chip on which the protective film is formed in the chip assembly on which the protective film is formed is separated from the dicing sheet and picked up, and the chip on which the protective film is formed is obtained. It has a chip acquisition process in which the obtained protective film is formed,

When the protective film-forming film is curable, the protective film is formed in a chip acquisition step in which the protective film is formed from after affixing the protective film-forming film to the back surface of the wafer in the first lamination step. The layered product (1), the layered product (2), the chip assembly on which the film for forming a protective film is formed, or the film for forming a protective film in the chip on which the film for forming a protective film is formed at any one step until after pickup of the chip on which the film for forming a protective film is formed. By curing to form a protective film, the method of manufacturing a chip with a protective film having a curing step of manufacturing the laminate 1 ′, the laminate 2 ′, the chip assembly with the protective film, or the chip with the protective film (this specification In this case, it is referred to as "manufacturing method 1").

The film for forming a protective film used in the first lamination step of the manufacturing method 1 is the film for forming a protective film according to an embodiment of the present invention described above.

In the first lamination step of Manufacturing Method 1, when the film for forming a protective film is curable, after affixing the film for forming a protective film on the back surface of the wafer, the film for forming a protective film after the affixing can be cured, thereby The laminated body 1'can be obtained. On the other hand, when the film for protective film formation is non-curable, the laminated body 1'is immediately obtained by affixing the film for protective film formation on the back surface of the wafer.

The dicing sheet used in the second lamination step of Manufacturing Method 1 may be a known one.

The curing step can be performed at any step as long as it is after affixing the protective film-forming film to the back surface of the wafer in the first lamination step. For example, the curing process is after obtaining the laminate 1 in the first lamination process; Between the first lamination process and the second lamination process; After obtaining the laminate 2 in the second lamination process; Between the second lamination process and the dividing/cutting process; After obtaining the chip assembly on which the film for forming a protective film was formed during the dividing/cutting process; Between the dividing/cutting process and the chip acquisition process on which the protective film is formed; It can be performed in any one after picking up the chip on which the film for protective film formation was formed during the chip acquisition process in which the protective film was formed.

When the film for forming a protective film is non-curable, Manufacturing Method 1 does not have the curing step.

In the manufacturing method 1, the curing of the film for forming a protective film is thermal curing or energy ray curing in any step. The conditions for thermal curing and energy ray curing at this time are as described above.

The first lamination process, the second lamination process, the dividing/cutting process, the chip acquisition process on which the protective film was formed, and the curing process in the manufacturing method 1 except that the film for forming a protective film according to the present embodiment is used. , It can be carried out in the same manner as in the case of a conventional method for manufacturing a chip with a protective film.

For example, the thickness of the wafer to which the protective film-forming film is affixed is not particularly limited, but it is preferably 20 to 600 µm, and more preferably 40 to 400 µm.

In the manufacturing method 1, the order of dividing the wafer in the dividing/cutting step and cutting the protective film-forming film or the protective film may be changed. In this specification, a method of manufacturing a chip with such a protective film is referred to as manufacturing method 2.

<<production method 2>>

That is, in the manufacturing method 2, through a process of cutting the protective film forming film in the layered body 2 and dividing the wafer according to the cut point of the protective film forming film to produce a chip, the chip and the A chip assembly having a protective film-forming film formed by holding a plurality of protective film-forming films formed on the dicing sheet after cutting formed on the back surface of the chip, or the laminated body (2') through a process of cutting the protective film and dividing the wafer according to the cut point of the protective film to produce a chip, and a plurality of pieces including the chip and the cut protective film formed on the back surface of the chip. A chip having a protective film is held on the dicing sheet, and a cutting/splitting process is provided to obtain a chip assembly with a protective film formed thereon.

Manufacturing Method 2 is the same as Manufacturing Method 1, except that it has a cutting/dividing process instead of a dividing/cutting process. That is, when manufacturing method 2 has the said 1st lamination process, the 2nd lamination process, the cutting/segmentation process, and the chip acquisition process in which the said protective film was formed, and the said protective film formation film is curable, further, Any one from after affixing of the protective film-forming film to the back surface of the wafer in the first lamination step to after picking up the chip on which the protective film-forming film is formed in the chip acquisition step on which the protective film is formed. In the step, the laminate (1), the laminate (2), the chip assembly on which the protective film-forming film is formed, or the protective film-forming film in the chip on which the protective film-forming film is formed is cured to form a protective film. '), the layered product 2', a chip assembly with a protective film, or a hardening step of producing a chip with a protective film.

<<production method 3>>

As a method of manufacturing a chip with a protective film formed by using the film for protective film formation together with a support sheet and affixing it to a wafer as a composite sheet for forming a protective film, for example,

A laminate (3) comprising a supporting sheet, a film for forming a protective film, and a wafer are laminated in this order in their thickness direction through a process of attaching the protective film forming film in the protective film forming composite sheet to the back surface of the wafer. ), or a lamination step of obtaining a laminate 3'configured by laminating a support sheet, a protective film, and a wafer in this order in the thickness direction thereof,

The chip and the cut-off protective film formed on the back surface of the chip through a process of dividing the wafer in the laminate 3 to produce a chip, and cutting the protective film-forming film according to the divided portions of the wafer. To obtain a chip assembly on which a film for forming a protective film is formed, consisting of a plurality of chips on which a film for forming a protective film having a forming film is formed is held on the support sheet, or by dividing the wafer in the laminate (3') A chip on which a plurality of protective films including the chip and the cut-off protective film formed on the back surface of the chip is formed is held on the support sheet through a process of manufacturing a chip and cutting the protective film according to the divided portions of the wafer. A dividing/cutting process to obtain a chip assembly with a protective film formed thereon,

The chip on which the protective film is formed in the chip assembly on which the protective film-forming film is formed, or the chip on which the protective film is formed in the chip assembly on which the protective film is formed is separated from the support sheet and picked up, to obtain a chip on which the protective film is formed. It has a chip acquisition process in which the obtained protective film is formed,

In the case where the protective film-forming film is curable, further, after affixing the protective film-forming film in the protective film-forming composite sheet to the back surface of the wafer in the laminating step, in the chip acquisition step in which the protective film is formed In any one step until after pickup of the chip on which the film for forming a protective film is formed, a film for forming a protective film among the stacked body (3), a chip assembly on which the film for forming a protective film is formed, or a chip on which the film for forming a protective film is formed is formed. By curing to form a protective film, a method for manufacturing a chip with a protective film having a curing step of producing the laminate 3 ′, a chip assembly with a protective film, or a chip with a protective film (in this specification, ``Manufacturing Method 3 It is referred to as "").

The film for forming a protective film used in the lamination process of the manufacturing method 3 is the film for forming a protective film according to an embodiment of the present invention described above.

In the lamination process of Manufacturing Method 3, when the protective film-forming film is curable, the protective film-forming composite sheet is affixed to the back surface of the wafer, and then the protective film-forming film in the protective film-forming composite sheet is cured. The laminated body 3'can be obtained by this.

On the other hand, when the film for forming a protective film is non-curable, the laminated body 3'is immediately obtained by affixing the composite sheet for forming a protective film on the back surface of the wafer.

The layered product 3 obtained in the lamination process of manufacturing method 3 is substantially the same as the layered product 2 obtained in the second lamination process of manufacturing method 1.

Similarly, the layered product 3'obtained in the lamination process of manufacturing method 3 is substantially the same as the layered product 2'obtained in the second lamination process of manufacturing method 1.

The curing step can be performed at any step as long as it is after affixing the protective film forming film in the protective film forming composite sheet to the back surface of the wafer in the lamination step. For example, the curing process is performed after obtaining the laminate 3 in the lamination process; Between the lamination process and the dividing/cutting process; After obtaining the chip assembly on which the film for forming a protective film was formed during the dividing/cutting process; Between the dividing/cutting process and the chip acquisition process on which the protective film is formed; It can be performed in any one after picking up the chip on which the film for protective film formation was formed during the chip acquisition process in which the protective film was formed.

When the film for forming a protective film is non-curable, Manufacturing Method 3 does not have the curing step.

In the manufacturing method 3, the curing of the film for forming a protective film is thermal curing or energy ray curing at any stage. The conditions for thermal curing and energy ray curing at this time are as described above.

Except for the use of the composite sheet for forming a protective film according to the present embodiment, the lamination process, the dividing/cutting process, the chip acquisition process with the protective film, and the curing process in the manufacturing method 3 are formed with a conventional protective film. It can be carried out in the same manner as in the case of the chip manufacturing method.

For example, the thickness of the wafer to which the composite sheet for forming a protective film is affixed is not particularly limited, but it is preferably 20 to 600 µm, and more preferably 40 to 400 µm.

<Other process>

Manufacturing method 1 is within a range that does not impair the effect of the present invention, in addition to each step of the first lamination process, the second lamination process, the division/cutting process, the chip acquisition process with the protective film, and the curing process, any of these It is also possible to have other processes that do not correspond to that.

Similarly, the manufacturing method 2 is within a range that does not impair the effect of the present invention, in addition to each of the steps of the first lamination process, the second lamination process, the cutting/splitting process, the chip acquisition process on which the protective film was formed, and the curing process, these You may have other processes that do not correspond to any of the above.

Similarly, manufacturing method 3 is within a range that does not impair the effect of the present invention, and does not correspond to any of these other than each of the above-described lamination process, division/cutting process, chip acquisition process on which the protective film is formed, and curing process. You may have another process.

In any of the manufacturing methods 1 to 3, the types of the other steps and the timing for performing them can be arbitrarily selected depending on the purpose, and are not particularly limited.

◇Method of manufacturing a substrate device

After obtaining the chip on which the protective film is formed by the above-described manufacturing method, the substrate device can be manufactured by the same method as the conventional manufacturing method, except that the chip on which the protective film is formed is used.

As a manufacturing method of such a substrate device, for example,

A chip arranging step of disposing the chip with the protective film on the circuit board by contacting the protruding electrode on the chip with the protective film obtained using the film for forming a protective film into contact with a connection pad on the circuit board;

By heating the chip on which the protective film is formed on the circuit board by using a halogen heater, the protruding electrode on the chip on which the protective film is formed is melted to improve the connection strength between the protruding electrode and the connection pad on the circuit board. The manufacturing method which has a flip-chip connection process to be made is mentioned.

In the substrate device obtained by the above manufacturing method, by using the chip on which the protective film is formed, the electrical connection strength between the protruding electrode and the connection pad on the circuit board becomes stronger than usual. For this reason, such a substrate device has high reliability.

This is because in the flip chip connecting step, as described above, the absorption amount of the near-infrared rays of the protective film in the chip on which the protective film is formed during heating is large, and the temperature of the protective film during heating is higher than usual. Due to the action of this protective film, which has become higher temperature, the protruding electrode on the chip on which the protective film is formed is also higher temperature, and the protruding electrode is likely to be melted under the influence, and as a result, electricity between the protruding electrode and the connection pad on the circuit board. The typical connection strength becomes stronger than usual.

In the flip-chip connection step, the maximum temperature reached at the time of heating of the protective film can be, for example, 250°C or higher, and may be set to any one of 260°C or higher, 270°C or higher, and 280°C or higher.

6 is a cross-sectional view schematically showing a state in which a chip on which a protective film is formed and a circuit board are electrically connected in the flip chip connecting step.

Here, the state in which the chip 901 on which the protective film is formed and the circuit board 8 are electrically connected is shown.

The chip 901 on which the protective film is formed includes a chip 9 and a cut protective film 130' formed on the rear surface 9b thereof. A plurality of protruding electrodes 91 are formed on the circuit surface 9a of the chip 9.

A plurality of connection pads 81 are formed on the circuit surface 8a of the circuit board 8.

One protruding electrode 91 on the chip 9 and one connection pad 81 on the circuit board 8 are in contact with each other, and the chip 901 on which the protective film is formed has a protective film 130 ′. As a result, since the protruding electrode 91 during heating is easier to dissolve than usual, the contact surface between the protruding electrode 91 and the connection pad 81 is wider than usual.

Incidentally, what is shown here is an example of a state in which the chip on which the protective film is formed is electrically connected to the circuit board, and the connection state is not limited to that shown here.

The chip arrangement step and flip chip connection step in the manufacturing method can be performed in the same manner as in the case of a conventional method for manufacturing a substrate device, except that a chip on which the protective film is formed is used.

For example, the heating of the chip on which the protective film is formed in the flip chip connecting step can be performed using, for example, a reflow furnace equipped with a halogen heater. At this time, the chip on which the protective film is formed can be heated by irradiating near-infrared rays in any one or all wavelength ranges of 1400 to 1500 nm, for example, using a halogen heater.

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 at all.

<Materials for manufacturing resin>

The official names of raw materials for producing resins abbreviated in this Example and Reference Example are shown below.

BA: n-butyl acrylate

MA: methyl acrylate

HEA: 2-hydroxyethyl acrylate

2EHA: acrylate-2-ethylhexyl

<Materials for manufacturing the composition for forming a protective film>

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

[Polymer component (A)]

(A)-1: Acrylic resin obtained by copolymerizing BA (45 parts by mass), MA (40 parts by mass), and HEA (15 parts by mass) (weight average molecular weight 500000, glass transition temperature -26°C)

[Thermosetting component (B1)]

(B1)-1: Bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "jER828", epoxy equivalent 184 to 194 g/eq)

(B1)-2: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "jER1055", epoxy equivalent 800 to 900 g/eq)

(B1)-3: Dicyclopentadiene type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 255 to 260 g/eq)

[Thermal Curing Agent (B2)]

(B2)-1: Dicyandiamide ("Adeka Hardener EH-3636AS" manufactured by ADEKA, thermally active latent epoxy resin curing agent, active hydrogen content 21 g/eq)

[Hardening accelerator (C)]

(C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemical Industry Co., Ltd. "Quazole 2PHZ")

[Filling material (D)]

(D)-1: Silica filler ("SC2050MA" manufactured by Adma-Tex, a silica filler surface-modified with an epoxy compound, average particle diameter 0.5 µm)

(D)-2: Spherical alumina (Showa Electric Corporation make "CB-P02J", average particle diameter 3.0 µm)

(D)-3: Silica filler ("YA050C-MJA" manufactured by Adma-Tex, average particle diameter 50 nm)

(D)-4: Stainless steel particles (particles obtained by pulverizing SUS304 to obtain an average particle diameter of 2.0 μm)

[Coupling agent (E)]

(E)-1:3-Aminopropyltrimethoxysilane ("A-1110" manufactured by Unica, Japan)

[Light absorber (I)]

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

(I)-2: Carbon black ("MA600" manufactured by Mitsubishi Chemical Corporation, average particle diameter 20 nm)

(I)-3: Copper (II) 2,3,9,10,16,17,23,24-octakis (octyloxy)-29H,31H-phthalocyanine (manufactured by Sigma-Aldrich)

(I)-4: Copper (II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (manufactured by Sigma Aldrich)

(I)-5:2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (manufactured by Sigma-Aldrich)

(I)-6: Dimonium-based dye ("CIR-1085F" manufactured by Carit, Japan, visible and infrared absorber)

[Example 1]

<Production of film for protective film formation>>

<Preparation of protective film-forming composition (III-1)>

Polymer component (A)-1 (150 parts by mass), thermosetting component (B1)-1 (60 parts by mass), (B1)-2 (20 parts by mass), (B1)-3 (20 parts by mass), (B2 )-1 (2.2 parts by mass), curing accelerator (C)-1 (2.2 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E)-1 (3 parts by mass), light absorber ( I)-1 (10 parts by mass) and light absorber (I)-2 (2.7 parts by mass) were dissolved or dispersed in methyl ethyl ketone, and stirred at 23° C., so that the total concentration of all components other than the solvent was 45 parts by mass. % Of the composition for forming a thermosetting protective film (III-1) was obtained. On the other hand, the blending amounts of components other than the solvent shown here are all blending amounts of the target substance not containing the solvent.

<Production of film for protective film formation>

Using a release film (2nd release film, "SP-PET50 1031" manufactured by Lintec Co., Ltd., thickness 50 µm), in which one side of the polyethylene terephthalate film was subjected to release treatment by silicone treatment, and the obtained release treatment surface was The composition for forming a protective film (III-1) was applied and dried at 100° C. for 2 minutes to prepare a film for forming a thermosetting protective film having a thickness of 25 μm.

Moreover, the peeling-treated surface of the peeling film (1st peeling film, "SP-PET38 1031" by Lintec Co., Ltd., 38 micrometers in thickness) was pasted on the exposed surface of the obtained protective film formation film on the side which does not have a 2nd peeling film By doing this, a laminated film comprising a protective film-forming film, a first release film formed on one side of the protective film-forming film, and a second release film formed on the other side of the protective film-forming film was obtained.

<<evaluation of protective film>>

<Measurement of X _max of the protective film>

The 1st peeling film was removed from the laminated film obtained above.

Subsequently, the first release film was removed in an air atmosphere, and the film for protective film formation provided with the second release film was heat-treated at 145° C. for 2 hours to heat-cure to form a protective film.

Subsequently, the second release film was removed from the protective film, and a UV-Vis spectrophotometer (``UV-VIS-NIR SPECTROPHOTOMETER UV-3600'' manufactured by Shimadzu Corporation) was used for the protective film, without using the integrating sphere attached thereto Absorbance was measured every 1 nm in a wavelength range of 1400 to 3200 nm including the near infrared region. _{And Xmax} was calculated|required from the measurement result. Table 1 shows the results.

<Measurement of S ₁₅₀ and S ₂₀₀ of the protective film>

The 1st peeling film was removed from the laminated film obtained above.

Next, the first release film was removed using an oven manufactured by SPEC Co., Ltd., and the film for protective film formation provided with the second release film was heat-treated at 145°C for 2 hours to form a protective film by heat curing.

Next, the second release film was removed from the protective film, and a differential scanning calorimeter ("PYRIS1" manufactured by Perkin Elmer) was used in accordance with JIS K 7123:2012, and the temperature rising rate was set to 10°C/min, and 40 to 250. In the temperature range of °C, the differential scanning calorific value of the protective film was measured under atmospheric pressure. Then, the heat flow at each temperature was calculated from the obtained heat flow chart, and S _{150 and S 200} of the protective film were calculated in consideration of the amount of use of the protective film. Table 1 shows the results.

<Calculation of Z ₁₅₀ and Z ₂₀₀ of the protective film>

_{Z 150} and Z ₂₀₀ were calculated from the values of _{X max} , S ₁₅₀ , and S ₂₀₀ obtained above. Table 1 shows the results.

<Measurement of T _m of the protective film>

The 1st peeling film was removed from the laminated film obtained above.

Subsequently, the first release film was removed in an air atmosphere, and the film for protective film formation provided with the second release film was heat-treated at 145° C. for 2 hours to heat-cure to form a protective film.

Subsequently, the second release film was removed from the protective film, and a UV-Vis spectrophotometer (“UV-VIS-NIR SPECTROPHOTOMETER UV-3600” manufactured by Shimadzu Corporation) was used for the protective film, and the integrating sphere attached thereto was not used, The transmittance of light was measured every 1 nm in a wavelength range of 400 to 750 nm (ie, visible light range). _{And T m} was calculated|required from the measurement result. Table 1 shows the results.

<Measurement of U _m of the protective film>

The 1st peeling film was removed from the laminated film obtained above.

Subsequently, the first release film was removed in an air atmosphere, and the film for protective film formation provided with the second release film was heat-treated at 145° C. for 2 hours to heat-cure to form a protective film.

Subsequently, the second release film was removed from the protective film, and a UV-Vis spectrophotometer (“UV-VIS-NIR SPECTROPHOTOMETER UV-3600” manufactured by Shimadzu Corporation) was used for the protective film to be 1400 to 2600 nm including the near-infrared region. In the wavelength range of, the total amount of reflected light of the total light was measured by the SCI method for every 1 nm of the specular reflected light (normally reflected light) and the diffusely reflected light. In addition, the amount of total light reflected light was measured in the same manner for the reference plate made of barium sulfate. In either case, the Shimadzu Corporation ``Large Sample Chamber MPC-3100'' is used as the sample folder, and the Shimadzu Corporation ``Integrating Sphere Attachment Device ISR-3100'' is used as the integrating sphere. The incident angle was set to 8°. And the ratio of the measured value in the protective film to the measured value in the reference plate ([measured value of the amount of light reflected from the protective film] / [measured value of the amount of light reflected from the reference plate] × 100), That is, the relative total light reflectance of the protective film was determined, and this was adopted as the reflectance of light. _{And U m} was calculated|required from the measurement result. Table 1 shows the results.

<Measurement of the maximum attainable temperature of the protective film during heating>

The first release film was removed from the laminated film obtained above, and the exposed surface of the film for forming a protective film thus formed corresponds to the back surface of an 8-inch silicon wafer (thickness 350 µm) having no bumps (protruding electrodes). It was affixed to the polished surface. In addition, the second release film was removed from the film for forming a protective film after the affixing, and a laminate 1 formed by laminating the film for forming a protective film and a silicon wafer was obtained (first lamination step).

Next, the laminated body 1 was heat-treated at 145°C for 2 hours using an oven manufactured by SPEC Co. to heat-cure the protective film-forming film to form a protective film (curing step).

Subsequently, after slow cooling the laminate 1 after heat curing, a dicing tape is affixed to the exposed surface of the protective film (i.e., the side opposite to the side on which the silicon wafer is formed) therein, so that the dicing tape ( Corresponding to the support sheet), a protective film, and a silicon wafer were laminated in this order in the thickness direction thereof to obtain a laminate 2'(2nd lamination step).

Subsequently, the silicon wafer in the laminate 2'is divided (diced) into a size of 20 mm x 20 mm using a dicing blade, and the protective film is also cut to the same size, so that the protective film after cutting is placed on the back surface. A silicon chip assembly in which a protective film was formed in which a number of the provided silicon chips were aligned on the dicing tape was prepared (dividing/cutting process).

Subsequently, the silicon chip on which the protective film was formed in the silicon chip assembly on which the protective film was formed was separated from the dicing tape and picked up (chip acquisition step with the protective film formed).

The silicon chip on which the picked up protective film was formed was placed on the conveyor. At this time, the silicon chip in the silicon chip on which the protective film was formed was brought into contact with the conveyor, the protective film was turned upward, and the protective film was fixed while bringing the thermocouple into contact with the protective film. The silicon chip on which the protective film was formed in this state was conveyed to the inside of a reflow furnace ("WL-15-20DNX type" manufactured by Sagami Science & Technology Co., Ltd.), and the silicon chip on which the protective film was formed was heated by using a halogen heater in this interior. . At this time, the output control knob (top surface NO. 2 output VR) of the halogen heater was set to 100, and the heat treatment conditions were practically provided.

And, using the said thermocouple, the maximum reaching temperature of the protective film at the time of heating by this halogen heater was measured. Table 1 shows the results.

<Production of film for protective film formation and evaluation of protective film>

[Examples 2 to 21, Reference Examples 1 to 6]

Any of the types and amounts of the components contained in the protective film-forming composition (III-1) in the preparation of the protective film-forming composition (III-1) so that the types and contents of the components contained in the protective film-forming composition (III-1) are as shown in Tables 1 to 4. Except for changing one or both, a protective film-forming film was produced in the same manner as in the case of Example 1, and the protective film was evaluated. The results are shown in Tables 1-4.

As is clear from the above results, in Examples 1 to 21, _{the maximum attainable temperature of the protective film at the time of X max} measurement was 254°C or higher, and was remarkably high. This is because the absorption amount of light in the wavelength region including the near infrared region of the protective film was large. When the temperature of the chip on which the protective film mounted on the circuit board is formed reaches such a region, it has been confirmed in advance that the solder bumps on the chip dissolve and the electrical connection strength between the chip and the connection pads on the circuit board is strengthened. In other words, it was confirmed that the chip provided with the protective film of Examples 1 to 21 on the back surface and the protective film formed with the solder bump on the circuit surface had a strong connection strength with a circuit board and a substrate device with remarkably high reliability. Could.

In Examples 1 to 21, Z ₁₅₀ was 0.39 or more, and Z ₂₀₀ was 0.37 or more.

In Examples 1 to 21, the number of light absorbers (I) contained in the protective film-forming film (composition (III-1)) was 2 to 7 types.

In Examples 1 to 21, in the composition (III-1), the ratio of the content of the light absorbing agent (I) to the total content of all components other than the solvent (that is, for forming a thermosetting protective film in a film for forming a thermosetting protective film) The content ratio of the light absorber (I) to the total mass of the film) was 2.2% by mass or more, and the ratio was on the high side. For this reason, in Examples 1 to 21, it was estimated that the amount of absorption of light in the wavelength region including the near infrared region was large.

In Examples 1 to 21, T _m was 2% or less, the transmittance of visible light was low, and the presence or absence of the protective film was easily visually recognized.

In addition, in Examples 1 to 21, U _m was 12% or less, and the reflectance of near-infrared rays was low. That is, the protective film-forming films of Examples 1 to 21 were capable of forming a protective film capable of easily increasing the temperature during heating and a protective film capable of suppressing malfunction of a device using near-infrared rays.

On the other hand, in Reference Examples 1 to 6, _{the maximum attainable temperature of the protective film} at the time of measuring X max was 248°C or less, and was lower than that of the example. This is because the absorption amount of light in the wavelength region including the near infrared region of the protective film cannot be said to be large. When the temperature of the chip on which the protective film mounted on the circuit board is formed is in such a region, the solder bump on the chip does not melt at all, or the melting is insufficient, and it is confirmed that the electrical connection strength between the chip and the connection pad on the circuit board is improved. I checked in advance that it does not work. That is, the chip provided with the protective film of Reference Examples 1 to 6 on the back surface and the protective film having the solder bumps formed on the circuit surface did not improve the connection strength with the circuit board and the reliability of the substrate device was not confirmed. I could confirm.

In Reference Examples 1 to 6, Z ₁₅₀ was 0.37 or less, and Z ₂₀₀ was 0.35 or less.

In Reference Examples 1 to 6, the number of light absorbers (I) contained in the protective film-forming film (composition (III-1)) was 2 to 4 types.

In Reference Examples 1 to 6, in the composition (III-1), the ratio of the content of the light absorbing agent (I) to the total content of all components other than the solvent (that is, for forming a thermosetting protective film in a film for forming a thermosetting protective film) The content ratio of the light absorber (I) to the total mass of the film) was 8.8% by mass or less, and the ratio was generally low.

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

[Example 1]

Using the film for forming a protective film obtained in Example 1 described above, a composite sheet for forming a protective film was then produced. More specifically, it is as follows.

On the other hand, in the present specification, hereinafter, as the numbers of the examples and reference examples at the time of manufacturing the composite sheet for forming a protective film, the examples and reference examples at the time of manufacturing the film for forming a protective film and evaluating the protective film described above. Use the number as it is.

<Production of adhesive composition (I-4)>

Contains an acrylic resin (100 parts by mass) and a trifunctional xylylene diisocyanate crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical) (10 parts by mass), and further contains methyl ethyl ketone as a solvent, other than the solvent A non-energy ray-curable pressure-sensitive adhesive composition (I-4) in which the total concentration of all components of was 25% by mass was prepared. On the other hand, the content of components other than methyl ethyl ketone shown here is the content of a target substance which does not contain a solvent.

The acrylic resin is an acrylic resin having a weight average molecular weight of 800000 obtained by copolymerizing acrylate-2-ethylhexyl (80 parts by mass) and acrylate-2-hydroxyethyl (20 parts by mass).

<Manufacture of supporting sheet>

Using a release film ("SP-PET38 1031" manufactured by Lintec, 38 µm in thickness), in which one side of the polyethylene terephthalate film was peeled off by silicone treatment, the pressure-sensitive adhesive composition (I- 4) was applied and heated and dried at 100° C. for 2 minutes to form a 5 μm-thick non-energy ray-curable pressure-sensitive adhesive layer.

Subsequently, a polypropylene film (1) (thickness 80 μm, colorless) having one side being a smooth side and the other side being an uneven side as a base material was used, and the non-energy ray-curable pressure-sensitive adhesive layer obtained above was used on the smooth side. The exposed surfaces of were bonded together. Thereby, the base material, the pressure-sensitive adhesive layer, and the release film were laminated in this order in their thickness direction to prepare a laminated sheet, that is, a support sheet with a release film formed thereon.

<Production of composite sheet for protective film formation>

The release film was removed from the support sheet obtained above. Moreover, the 1st peeling film was removed from the laminated film obtained in Example 1 (that is, the film for protective film formation provided with a 1st peeling film and a 2nd peeling film). And, by bonding the exposed surface of the pressure-sensitive adhesive layer formed by removing the release film and the exposed surface of the protective film-forming film formed by removing the first release film, the substrate, the pressure-sensitive adhesive layer, the protective film-forming film, and the second release film In this procedure, a composite sheet for forming a protective film formed by being laminated in the thickness direction was produced.

[Examples 2 to 21, Reference Examples 1 to 6]

In place of the laminated film obtained in Example 1, a composite sheet for forming a protective film was produced in the same manner as in the case of Example 1, except that the laminated films obtained in Examples 2 to 21 and Reference Examples 1 to 6 were used.

<<evaluation of protective film>>

<Measurement of X _max , S ₁₅₀ , S ₂₀₀ , T _m and U _m of the _{protective film and calculation of Z 150} and Z ₂₀₀ of the protective film>

_{X max} , S ₁₅₀ , S ₂₀₀ of the protective film in the same manner as in Example 5 except that the composite sheet for forming a protective film obtained in Example 5 was used instead of the laminated film in Example 5 above. , T _m and U _m were measured to calculate _{Z 150} and Z _{200 of the protective film.} For example, _{at the time of measurement of X max} , the second release film is removed from the composite sheet for forming a protective film, and the film for forming a protective film in the composite sheet for forming a protective film in this state is heat-treated at 145° C. for 2 hours to heat cure. To form a protective film. Then, the laminate of the substrate and the pressure-sensitive adhesive layer (that is, the supporting sheet) was removed from the protective film, and the absorbance was measured in a wavelength range of 1400 to 3200 nm for the protective film. Also at the time of measurement of S ₁₅₀ , S ₂₀₀ , T _m and U _m , the formation of a protective film and measurement of these physical properties of the protective film were similarly performed.

<Measurement of the maximum attainable temperature of the protective film during heating>

The second release film was removed from the composite sheet for forming a protective film obtained in Example 5, and the exposed surface of the film for forming a protective film formed thereby was an 8-inch silicon wafer without bumps (protruding electrodes) (thickness: 350 μm). It was affixed to the polished surface corresponding to the back surface of.

Next, using an oven manufactured by SPEC Co., Ltd., the silicon wafer provided with the composite sheet for forming a protective film was heat-treated at 145°C for 2 hours to thermally cure the film for forming a protective film to form a protective film (curing step). Thereby, a support sheet, a protective film, and a silicon wafer were laminated in this order in the thickness direction, and the laminated body 3'was obtained (lamination process).

Thereafter, except that this laminate (3') was used, the silicon wafer was divided (dicing), the protective film was cut (above, the dividing/cutting process), and the protective film was formed in the same manner as in the case of Example 5. The chip was picked up (a chip acquisition process in which the protective film was formed), and the maximum reached temperature of the protective film was measured.

As a result, all of the evaluation results of the protective film in the case of using the composite sheet for forming a protective film here are completely the same or an error of negligible degree when compared with the evaluation results in Example 5 using the laminated film. It was made to be almost equivalent, and was practically the same.

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

101, 102, 103, 104... Composite sheet for forming a protective film, 10, 11... Support sheet, 10a, 20a... One side of the support sheet (first side), 11... Substrate, 11a... One side of the substrate (first side), 12... Pressure-sensitive adhesive layer, 13, 23... Film for forming a protective film, 130'... Protective film after cutting, 9... Chip, 9b... The back side of the chip

Claims (8)

As a film for forming a protective film for forming a protective film on the back surface of the chip,
_{Using the maximum absorbance value (X max} ) of the protective film at a wavelength of 1400 to 1500 nm _{and the specific heat (S 150} ) at 150° C. of the protective film, the equation:
Z ₁₅₀ ＝X _max ／S _{150
Z 150} calculated by is 0.38 or more, and,
Using the X _max and the specific heat at 200° C. of the protective film (S ₂₀₀ ), the formula:
Z ₂₀₀ ＝X _max ／S ₂₀₀
The film for forming a protective film in which Z _{200 calculated by is 0.33 or more.} The method of claim 1,
The protective film-forming film is thermosetting or energy ray-curable film for forming a protective film. The method according to claim 1 or 2,
The film for forming a protective film, wherein the film for forming a protective film contains two or more types of light absorbers capable of absorbing any one or both of visible light and infrared light. The method according to claim 1 or 2,
The film for forming a protective film, wherein the film for forming a protective film contains a carbon material. The method according to any one of claims 1 to 4,
A film for forming a protective film in which _{the minimum value (T m} ) of the transmittance of light having a wavelength of 400 to 750 nm of the protective film is 15% or less. The method according to any one of claims 1 to 5,
A film for forming a protective film in which _{the maximum value (U m} ) of the reflectance of light having a wavelength of 1400 to 1500 nm of the protective film is 20% or less. A support sheet and a film for forming a protective film formed on one side of the support sheet,
The composite sheet for forming a protective film, wherein the film for forming a protective film is the film for forming a protective film according to any one of claims 1 to 6. The method of claim 7,
The support sheet includes a substrate and an adhesive layer formed on one side of the substrate,
The composite sheet for forming a protective film, wherein the pressure-sensitive adhesive layer is disposed between the substrate and the film for forming a protective film.

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