JP2021061321A - Protective film forming film and protective film forming composite sheet - Google Patents

Abstract

To provide a protective film forming film of the back surface of a chip for protecting the back surface of a flip chip, and a protective film forming composite sheet.SOLUTION: In a protective film forming composite sheet 101, a protective film forming film 13 for forming a protective film on the back surface of a chip, Z150 calculated by a formula: Z150=Xmax/S150 using the maximum absorbance Xmax at wavelengths of 1400 to 1500 nm of the protective film, and the specific heat S150 of the protective film at 150°C is 0.38 or more, and Z200 calculated by a formula: Z200=Xmax/S200 using the Xmax, and the specific heat S200 of the protective film at 200°C is 0.33 or more. Further, a protective film forming film is provided on the surface of a support sheet 10.SELECTED DRAWING: Figure 2

Description

The present invention relates to a protective film forming film and a protective film forming composite sheet.

Some wafers such as semiconductor wafers and insulator wafers have a circuit formed on one surface (circuit surface) and further have a protruding electrode such as a bump on the surface (circuit surface). Such a wafer is divided into chips, and the projecting electrodes are connected to a connection pad on the circuit board to be mounted on the circuit board.
In such wafers and chips, the surface (rear surface) opposite to the circuit surface may be protected by a protective film in order to suppress damage such as cracks (see Patent Documents 1 and 2). ..

In order to form such a protective film, a protective film forming film for forming the protective film is attached to the back surface of the semiconductor wafer. At this time, on one surface of the support sheet and the support sheet. A protective film-forming composite sheet provided with the protective film-forming film provided in the above can be used. The support sheet can be used as a dicing sheet for fixing the protective film-forming film or a wafer having the protective film on the back surface when the wafer is divided into chips.

JP-A-2015-32644 International Publication No. 2015/146936

As described above, the circuit board on which the chip is mounted is used as a substrate device in various electronic components, and improves the electrical connection strength between the protruding electrode of the chip and the connection pad on the circuit board. As a result, a more reliable substrate device can be manufactured.
On the other hand, Patent Documents 1 and 2 do not disclose means for further improving such connection strength.

The present invention relates to a protective film forming film for forming a protective film on the back surface of the chip, and as a protective film forming composite sheet provided with the protective film forming film, the protruding electrode of the chip and the circuit board. It is an object of the present invention to provide a connection pad and a device capable of improving the electrical connection strength of the connection pad.

The present invention is a protective film forming film for forming a protective film on the back surface of the chip.
Using the maximum value _{X max} of the absorbance at a wavelength 1400~1500nm of the protective film, and a specific heat _{S 0.99} at 0.99 ° C. of the protective film, wherein:
Z ₁₅₀ = X _max / S _{150
Z 150} calculated by is 0.38 or more and
Wherein the _{X max,} the specific heat _{S 200} at 200 ° C. of the protective film, using the formula:
Z ₂₀₀ = X _max / S ₂₀₀
Provided is a protective film forming film in which Z _{200 calculated by the above is 0.33 or more.}
The protective film forming film of the present invention may be thermosetting or energy ray curable.

The protective film forming film of the present invention may contain two or more kinds of light absorbers capable of absorbing either one or both of visible light and infrared rays.
The protective film forming film of the present invention may contain a carbon material.
In the protective film forming film of the present invention, the protective layer, the minimum value _{T m} of a transmittance of light having a wavelength of 400~750nm is preferably 15% or less.
In the protective film forming film of the present invention, the protective layer, the maximum value _{U m} of the reflectance of light of wavelength 1400~1500nm is preferably 20% or less.

The present invention includes a support sheet and a protective film-forming film provided on one surface of the support sheet, and the protective film-forming film is the protective film-forming film of the present invention. A composite sheet for forming a protective film is provided.
In the composite sheet for forming a protective film of the present invention, the support sheet includes a base material and an adhesive layer provided on one surface of the base material, and the pressure-sensitive adhesive layer is the said. It may be arranged between the base material and the protective film forming film.

According to the present invention, as a protective film forming film for forming a protective film on the back surface of the chip and a protective film forming composite sheet provided with the protective film forming film, the protruding electrode of the chip and the circuit board A connection pad and one capable of improving the electrical connection strength of the connection pad are provided.

It is sectional drawing which shows typically an example of the film for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically an example of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically another example of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows still another example schematically of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows still another example schematically of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically an example of the connection state of a chip with a protective film and a circuit board when the protective film forming film which concerns on one Embodiment of this invention is used.

Protective film forming film The protective film forming film according to an embodiment of the present invention is a protective film forming film for forming a protective film on the back surface of a chip, and the protective film has a wavelength of 1400 to 1500 nm. Using the maximum value X _{max of the absorbance and the specific heat S 150} of the protective film at 150 ° C., the formula:
Z ₁₅₀ = X _max / S _{150
Z 150} calculated by is 0.38 or more and
Wherein the _{X max,} the specific heat _{S 200} at 200 ° C. of the protective film, using the formula:
Z ₂₀₀ = X _max / S _{200
Z 200} calculated by is 0.33 or more.
The protective film-forming film of the present embodiment can form a protective film-forming composite sheet by laminating it with a support sheet, for example, as will be described later.

The protective film forming film of the present embodiment is a film used to protect the chip by providing a protective film on the back surface of the chip.
The protective film-forming film is soft and can be attached to a wafer before it is divided into chips.

The protective film forming film of the present embodiment may be curable or non-curable. That is, the protective film forming film may function as a protective film by its curing, or may function as a protective film in an uncured state.
The curable protective film forming film may be either thermosetting or energy ray curable, and may have both thermosetting and energy ray curable properties.

As used herein, the term "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum. Examples of energy rays include ultraviolet rays, radiation, electron beams and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
Further, in the present specification, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" is a property of not being cured by irradiating with energy rays. Means.
Further, "non-curable" means a property of not being cured by any means such as heating or irradiation with energy rays. The non-curable protective film forming film is regarded as a protective film after the stage of being provided (formed) on the target object.

In the present specification, the "wafer" is a semiconductor wafer composed of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; sapphire, glass, and the like. An insulator wafer composed of an insulator can be mentioned.
A circuit is formed on one surface of these wafers, and in the present specification, the surface of the wafer on which the circuit is formed is referred to as a "circuit surface". The surface of the wafer opposite to the circuit surface is referred to as the "back surface".
The wafer is divided into chips by means such as dicing. In the present specification, as in the case of the wafer, the surface of the chip on the side where the circuit is formed is referred to as a “circuit surface”, and the surface on the side opposite to the circuit surface of the chip is referred to as a “back surface”.
Both the circuit surface of the wafer and the circuit surface of the chip are provided with protruding electrodes such as bumps and pillars. The projecting electrode is preferably made of solder.

By using the protective film forming film of the present embodiment or the protective film forming composite sheet provided with the protective film forming film, a chip provided with a protective film on the back surface (referred to as a "chip with a protective film" in the present specification). There is) can be manufactured.

Further, the substrate device can be manufactured by using the chip with the protective film.
As used herein, the term "board device" means a chip having a protective film, which is formed by flip-chip connecting a chip with a protective film to a connection pad on a circuit board at a protruding electrode on the circuit surface. For example, when a semiconductor wafer is used as the wafer, a semiconductor device can be mentioned as the substrate device.
In the process of manufacturing a substrate device, a reflow furnace equipped with a halogen heater is used to heat a circuit board on which a chip with a protective film is mounted to melt a protruding electrode on the chip with a protective film, thereby melting the protruding electrode. And, the electrical connection between the connection pad on the circuit board and the connection pad may be strengthened.

The protective film obtained from the protective film forming film of the present embodiment has a Z ₁₅₀ of 0.38 or more and a Z ₂₀₀ of 0.33 or more. The amount of absorption is large and the temperature during heating is higher than usual. Therefore, due to the action of this protective film, which has become hotter, the protruding electrode on the chip with the protective film also becomes hotter, and as a result, the protruding electrode As a result, the electrical connection strength between the protruding electrode and the connection pad on the circuit board becomes stronger than usual.
By using a circuit board on which such a chip is mounted, a highly reliable board device can be manufactured.

Z ₁₅₀ (= X _max / S ₁₅₀ ) of the protective film is an index showing the ease of temperature rise of the protective film at 150 ° C., and is 0.38 or more, for example, 0.41 or more, 0. It may be any one of .45 or more, 0.55 or more, 0.65 or more, 0.8 or more, 1.2 or more, 1.5 or more, 2 or more, and 2.5 or more. When Z ₁₅₀ is at least the lower limit value, 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. The Z ₁₅₀ is preferably 4.2 or less in that it is easier to form a protective film satisfying the above conditions of the Z _150.

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

Z ₂₀₀ (= X _max / S ₂₀₀ ) of the protective film is an index showing the ease of temperature rise of the protective film at 200 ° C., and is 0.33 or more, and 0.35 or more. Preferably, for example, 0.4 or more, 0.45 or more, 0.52 or more, 0.6 or more, 0.8 or more, 1.2 or more, 1.4 or more, 1.9 or more, and 2.4 or more. It may be either. When Z ₂₀₀ is at least the lower limit value, 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. The Z ₂₀₀ is preferably 4 or less in that it is easier to form a protective film satisfying the above conditions of the Z _200.

The Z ₂₀₀ can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. 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. It may be any of 52 to 4, 0.6 to 4, 0.8 to 4, 1.2 to 4, 1.4 to 4, 1.9 to 4, and 2.4 to 4. However, these are examples of the _{Z 200.}

The reason for specifying the protective film forming film of the present embodiment by using the specific heats of the protective film at 150 ° C. and 200 ° C. is that when the circuit board on which the chip with the protective film is mounted is heated, the temperature is as high as 250 ° C. or higher. This is because the chip with the protective film always passes the heating at the temperatures of 150 ° C. and 200 ° C. at that time.

_{The maximum value X max} of the absorbance of the protective film at a wavelength of 1400 to 1500 nm is not particularly limited as long as the above conditions of Z ₁₅₀ and Z _{200 are satisfied.}
X _max is preferably 0.4 or more, more preferably 0.5 or more, for example, 0.6 or more, 0.9 or more, 1.2 or more, 1.6 or more, 2 or more, It may be either 2.4 or more and 2.8 or more.
X _max is preferably 4.5 or less, for example, 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. It may be either. The _{protective film having X max} equal to or less than the upper limit value is easier to form, and when near-infrared rays are irradiated, only the surface of the irradiated portion and its vicinity are instantly rapidly heated, and as a result. , The phenomenon that the surface of the irradiation site is discolored or roughened can be highly suppressed.

X _max can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and any of the upper limit values. 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. Any of 9-4.5, 1.2-4.5, 1.6-4.5, 2-4.5, 2.4-4.5, and 2.8-4.5. Also, 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 0.4. It may be any of 1.5, 0.4 to 1.4, 0.4 to 1.2, and 0.4 to 0.99. However, these are examples of _Xmax.

_{The specific heat S 150} of the protective film at 150 ° C. is not particularly limited as long as the above-mentioned _{conditions of Z 150 are 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, for example, 1.65. It may be as follows.

S ₁₅₀ can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and any of the upper limit values. For example, in one embodiment, S ₁₅₀ is preferably 1-2, more preferably 1-1.9, even more preferably 1-1.8, 1-1.7. It is particularly preferable to have, for example, 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 above-mentioned _{conditions of Z 200 are 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, further preferably 1.9 or less, particularly preferably 1.8 or less, for example, 1.75. It may be as follows.

The S ₂₀₀ can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and any of the upper limit values. For example, in one _{embodiment, S 200} is preferably 1.1 to 2.1, more preferably from 1.1 to 2, more preferably from 1.1 to 1.9, It is particularly preferably 1.1 to 1.8, and may be, for example, 1.1 to 1.75. However, these are examples of _S200.

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

Of the protective film, the minimum value _{T m} of a transmittance of light having a wavelength of 400~750nm is not particularly limited, but is preferably 15% or less, more preferably 10% or less, is less than 7% It is more preferable, and it is particularly preferable that it is 4% or less. When T _m is equal to or less than the upper limit value, the presence or absence of the protective film can be more easily visually recognized.
The lower limit of the T _m is not particularly limited, for example, the T _m may be 0% or more.

Of the protective film, the maximum value _{U m} of the reflectance of light of wavelength 1400~1500nm is not particularly limited, but is preferably 20% or less, more preferably 15% or less, is 12% or less Is even more preferable. When U _m is not more than the upper limit value, the temperature of the protective film can be easily raised when the circuit board on which the above-mentioned chip with the protective film is mounted is heated. In addition, when a chip with a protective film is used, it is possible to prevent a device that uses near infrared rays, such as a near infrared ray reflection sensor, from malfunctioning.
The lower limit of U _m is not particularly limited, for example, U _m may be 0% or more. In terms of forming the condition is satisfied protective film U _m is easier is preferably U _m is not less than 0.2%, more preferably 0.5% or more, more than 1% It is more preferable to have.
The light reflectance of the protective film can be measured by the method described in Examples described later.

In the present embodiment, _{the protective film defining X max} , S ₁₅₀ and S ₂₀₀ described above is obtained by heat-treating the protective film-forming film at 145 ° C. for 2 hours when the protective film-forming film is thermosetting. It is preferable that the film is a cured product obtained by the above, and when the protective film forming film is energy ray curable, the protective film forming film is provided under the conditions of an ^{illuminance of 280 mW / cm 2} and a light amount of 260 mJ / cm ^2. It is preferably a cured product obtained by irradiating the film with energy rays twice.
On the other hand, when the protective film-forming film is non-curable, _{the protective film defining Xmax} , S ₁₅₀ and S ₂₀₀ described above is the protective film-forming film itself.

In the present embodiment, when calculating the _{above-mentioned Z 150} , those measured using the same type of protective film are adopted as _{X max} and S _150. Similarly, when calculating the above-mentioned Z ₂₀₀ , those measured using the same type of protective film are adopted as _{X max} and S _200.

When the protective film-forming film is thermoset to form a protective film, unlike the case where the protective film is cured by irradiation with energy rays, the protective film-forming film is heated even if its thickness becomes thicker. Since it is sufficiently cured, a protective film having high protective performance can be formed. Further, by using a normal heating means such as a heating oven, a large number of protective film forming films can be collectively heated and thermoset.
When the protective film-forming film is cured by irradiation with energy rays to form a protective film, unlike the case of thermosetting, the protective film-forming composite sheet does not need to have heat resistance and has a wide range. It is possible to construct a composite sheet for forming a protective film. In addition, it can be cured in a short time by irradiating with energy rays.
When the protective film-forming film is used as a protective film without being cured, the curing step can be omitted, so that a chip with a protective film can be manufactured by a simplified process.

The protective film forming film is preferably thermosetting or energy ray curable.

Protects the protective film-forming film regardless of whether it is curable or non-curable, and if it is curable, whether it is thermosetting or energy ray curable. The film-forming film may be composed of one layer (single layer) or may be composed of two or more layers. When the protective film forming film is composed of 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.
When the protective film forming film is composed of two or more layers, the adhesiveness between the layers is inferior, or the protective film is warped due to the difference in the easiness of expansion and contraction of each layer, and the protective film is formed. However, there is a possibility that defects such as peeling from the back surface of the chip may occur, and in terms of suppressing such defects, the protective film forming film is preferably composed of one layer.

In the present specification, not only in the case of a film for forming a protective film, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers may be the same". It means that "they may be different, or only some of the layers may be the same", and "multiple layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other". It means that.

Protective film regardless of whether the protective film forming film is curable or non-curable, and if it is curable, whether it is thermosetting or energy ray curable. The thickness of the forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, particularly preferably 5 to 60 μm, and for example, 10 to 50 μm, 15 to 40 μm, 17 to 38 μm. , And may be any of 20 to 30 μm. When the thickness of the protective film forming film is at least the above lower limit value, it is possible to form a protective film having a higher protective ability, and it is easier to form a protective film having a high absorbance. When the thickness of the protective film forming film is not more than the upper limit value, it is possible to prevent the film from becoming excessively thick, and the temperature of the protective film when the temperature rises is 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 a plurality of layers means the protective film forming film. It means the total thickness of all the layers that make up.

<< Composition for forming a protective film >>
The protective film-forming film can be formed by using a protective film-forming composition containing the constituent material. For example, a protective film-forming film can be formed by applying a protective film-forming composition to the surface to be formed and drying it if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the protective film-forming composition is usually the same as the ratio of the contents of the components in the protective film-forming film. In the present specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The thermosetting protective film forming film can be formed by using the thermosetting protective film forming composition, and the energy ray curable protective film forming film is formed by using the energy ray curable protective film forming composition. The film for forming a non-curable protective film can be formed by using a composition for forming a non-curable protective film. In the present specification, when the protective film-forming film has both thermosetting and energy ray-curable properties, the thermosetting of the protective film-forming film contributes to the formation of the protective film. If the contribution is greater than the contribution of energy ray curing, the protective film forming film is treated as thermosetting. On the contrary, when the contribution of the energy ray curing of the protective film forming film to the formation of the protective film is larger than the contribution of thermosetting, the protective film forming film is treated as one of energy ray curing.

The composition for forming a protective film may be applied 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, and the like. A method using various coaters such as a screen coater, a Meyer bar coater, and a knife coater can be mentioned.

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

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.

◎ Thermosetting protective film forming film The curing conditions for forming a protective film by thermosetting the thermosetting protective film forming film are such that the protective film fully exerts its function. As long as it is not particularly limited, it may be appropriately selected depending on the type of the thermosetting protective film forming film.
For example, the heating temperature of the thermosetting protective film forming film at the time of thermosetting is preferably 100 to 200 ° C., more preferably 110 to 170 ° C., and particularly preferably 120 to 150 ° C. .. The heating time during the thermosetting is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.
The protective film formed by thermosetting is preferably slowly cooled to room temperature. The slow cooling method is not particularly limited, and may be allowed to cool.

A protective film forming film at room temperature is heated to a temperature exceeding room temperature and then cooled to room temperature to obtain a protective film forming film after heating and cooling, and for forming a protective film after heating and cooling. When the hardness of the film and the hardness of the protective film forming film before heating are compared at the same temperature, if the protective film forming film after heating and cooling is harder, this protective film forming film is used. , Thermocurable.

Preferred thermosetting protective film forming films include, for example, those containing a polymer component (A), a thermosetting component (B) and a light absorber (I).
The polymer component (A) is a component that can be regarded as being formed by a polymerization reaction of a polymerizable compound.
The thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction using heat as a trigger for the reaction. In the present specification, the polymerization reaction also includes a polycondensation reaction.

<Composition for forming a thermosetting protective film (III-1)>
As a preferable composition for forming a thermosetting protective film, for example, a composition for forming a thermosetting protective film containing the polymer component (A), the thermosetting component (B) and the light absorber (I) ( III-1) (in this specification, it may be simply abbreviated as "composition (III-1)") and the like.

[Polymer component (A)]
The polymer component (A) imparts film-forming property, flexibility, toughness, malleability, etc. to the thermosetting protective film forming film, and imparts flexibility, toughness, malleability, etc. to the protective film. It is a component of.
The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

Examples of the polymer component (A) include acrylic resin, thermoplastic polyester resin, thermoplastic urethane resin, acrylic urethane resin, silicone resin, rubber resin, phenoxy resin, thermoplastic polyimide and the like. Acrylic resin is preferable.

Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 1000 to 2000000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. Further, when the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the film for forming a thermosetting protective film easily follows the uneven surface of the adherend, and the adherend and the thermosetting protective film are formed. The generation of voids and the like between the film and the film is further suppressed.
In the present specification, the "weight average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, more preferably -30 to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, for example, the adhesive force 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 not more than the above upper limit value, the adhesive force between the thermosetting protective film forming film and the cured product thereof is improved.

The acrylic resin has m-type (m is an integer of 2 or more) constituent units, and for each of the m-type monomers that induce these constituent units, any of the non-overlapping numbers from 1 to m. Is sequentially assigned and named as "monomer m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox formula shown below.

（式中、Ｔｇはアクリル系樹脂のガラス転移温度であり；ｍは２以上の整数であり；Ｔｇ_ｋはモノマーｍのホモポリマーのガラス転移温度であり；Ｗ_ｋはアクリル系樹脂における、モノマーｍから誘導された構成単位ｍの質量分率であり、ただし、Ｗ_ｋは下記式を満たす。）

(In the formula, 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 monomer m in the acrylic resin. It is a mass fraction of the structural unit m derived from, where W _k satisfies the following equation.)

（式中、ｍ及びＷ_ｋは、前記と同じである。）

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

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

Examples of the acrylic resin include a polymer of one or more (meth) acrylic acid esters; one or more (meth) acrylic acid esters, and (meth) acrylic acid, itaconic acid, and acetic acid. Examples thereof include a copolymer of one or more monomers selected from vinyl, acrylonitrile, styrene, N-methylol acrylamide, and the like.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth). ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , (Meta) undecyl acrylate, (meth) dodecyl acrylate ((meth) lauryl acrylate), (meth) tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), (meth) acrylate Alkyl groups constituting alkyl esters such as pentadecyl, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc. (Meta) acrylic acid alkyl ester having a chain structure with 1 to 18 carbon atoms;
(Meta) Acrylic acid cycloalkyl esters such as (meth) acrylate isobornyl, (meth) acrylate dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meta) Acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meta) acrylate imide;
A glycidyl group-containing (meth) acrylic acid ester 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-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylic acid. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom.

The monomer constituting the acrylic resin may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound without a cross-linking 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 the acrylic resin (hereinafter, may be simply abbreviated as “thermoplastic resin”) is used alone without using the acrylic resin. Alternatively, it may be used in combination with an acrylic resin. By using the thermoplastic resin, the peelability of the protective film from the support sheet is improved, and the film for forming the thermosetting protective film easily follows the uneven surface of the adherend, so that the adherend and the thermosetting are thermally cured. The generation of voids and the like may be further suppressed with the film for forming the sex protective film.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.

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, polystyrene and the like.

The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected.

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all the components other than the solvent (that is, formation of a thermosetting protective film in the film for forming a thermosetting protective film). The ratio of the content of the polymer component (A) to the total mass of the film for use) is preferably 5 to 80% by mass, preferably 8 to 70% by mass, regardless of the type of the polymer component (A). It is more preferably 11 to 60% by mass, particularly preferably 14 to 50% by mass, and for example, 17 to 45% by mass and 20 to 40% by mass. May be good.
Since the protective film forming film and the protective film are usually thin, when a protective film forming film or a protective film having low toughness and brittleness is used, it is used for forming the protective film at the time of manufacturing the chip with the protective film. Cracks (gap) occur in the film or protective film. In that case, when the finally manufactured chip with a protective film is heated, the heat transfer effect from the high temperature protective film to the protruding electrode on the chip may decrease. However, when the ratio is at least the lower limit value, the toughness of the protective film forming film and the protective film becomes higher, and the effect of suppressing such a defect becomes higher.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains a component corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is used. , The polymer component (A) and the thermosetting component (B) are considered to be contained.

[Thermosetting component (B)]
The thermosetting component (B) is a component for curing a film for forming a thermosetting protective film.
The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, two or more types, or two or more types. If, the combination and ratio thereof can be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethane-based curable resins, unsaturated polyester-based curable resins, silicone-based curable resins, and the like. Thermosetting resins are preferred.

(Epoxy thermosetting resin)
The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy-based thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, two or more types, or two or more types. If so, their combinations and ratios can be arbitrarily selected.

・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, and dicyclopentadiene 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 functional epoxy compounds can be mentioned.

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 the polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, and a (meth) group. Examples thereof include an acrylamide group, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30,000 from the viewpoint of the curability of the thermosetting protective film forming film and the strength and heat resistance of the cured protective film. It is preferably 300 to 10000, more preferably 300 to 3000, and 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 the epoxy resin (B1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is annealed, and the like, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

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

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. , 400 to 10000, more preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, but is preferably 60 to 500, for example.

As the thermosetting agent (B2), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio 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 0.1 to 500 mass by mass with respect to 100 parts by mass of the content of the thermosetting resin (B1). It is preferably 0.1 to 200 parts by mass, further preferably 0.1 to 100 parts by mass, and particularly preferably 0.5 to 50 parts by mass, for example. , 0.5 to 25 parts by mass, 0.5 to 10 parts by mass, and 0.5 to 5 parts by mass. When the content of the thermosetting agent (B2) is at least the lower limit value, the curing of the thermosetting protective film forming film becomes easier to proceed. When the content of the thermosetting agent (B2) is not more than the upper limit value, the hygroscopicity of the thermosetting protective film forming film is reduced, and the package obtained by using the protective film forming composite sheet is used. The reliability 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 determined. The content of the polymer component (A) is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, for example, 30 to 100 parts by mass and 40 to 80 parts by mass with respect to 100 parts by mass. It may be any of 50 parts by mass and 50 to 70 parts by mass. When the content of the thermosetting component (B) is in such a range, for example, the adhesive force between the cured product of the protective film forming film and the support sheet is suppressed, and the peelability of the support sheet is improved. To do.

[Light Absorbent (I)]
The light absorber (I) is a component that facilitates the temperature rise of the protective film by absorbing light in a state of being present in the protective film.
Since the composition (III-1) and the thermosetting protective film forming film contain the light absorber (I), the X _max of the protective film becomes larger, and Z ₁₅₀ and Z ₂₀₀ become larger. Will be easier. Further, since the transmittance of the protective film for light having a wavelength of 400 to 750 nm is reduced, the presence or absence of the protective film can be easily visually recognized.

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

Examples of the organic pigment include diimonium pigment, aminium pigment, cyanine pigment, merocyanine pigment, croconium pigment, squalium pigment, azulenium pigment, polymethine pigment, naphthoquinone pigment, pyrylium pigment, and phthalocyanine pigment. Dyes, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, Pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indolphenol pigments, triallylmethane pigments, anthraquinone pigments, dioxazine pigments, naphthol pigments, azomethine pigments. , Benzimidazolone pigments, spirone pigments, pyranthron pigments, slene pigments and the like.

Examples of the inorganic pigment include carbon materials such as carbon black; lanthanum-based materials; tin-based materials; antimony-based materials; and tungsten-based materials. Here, the lanthanum-based material, the tin-based material, the antimony-based material, and the 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.

The light absorber (I) preferably can absorb either one or both of visible light and infrared light.

The light absorber (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected. For example, the composition (III-1) and the film for forming a thermosetting protective film may contain one or more organic pigments as the light absorber (I), or may contain only inorganic pigments. It may contain one kind or two or more kinds, or may contain one kind or two or more kinds of both organic pigments and inorganic pigments.

The composition (III-1) and the film for forming a thermosetting protective film preferably contain two or more kinds of light absorbers (I) capable of absorbing either one or both of visible light and infrared rays. It is more preferable to contain ~ 7 kinds.

When the composition (III-1) and the film for forming a thermosetting protective film contain an inorganic pigment as the light absorber (I), it preferably contains a carbon material, in which case, for example, a carbon material and It may contain both organic dyes.

In the composition (III-1), the ratio of the content of the light absorber (I) to the total content of all the components other than the solvent (that is, the heat-curable protective film in the film for forming the heat-curable protective film). The ratio of the content of the light absorber (I) to the total mass of the forming film) is preferably 0.1 to 20% by mass, more preferably 0.3 to 17.5% by mass. , 0.5 to 16% by mass, more preferably 1 to 15% by mass. When the ratio is at least the lower limit value, the effect of using the light absorber (I) can be obtained more remarkably. When the ratio is not more than the upper limit value, the excessive use of the light absorber (I) is suppressed.

[Curing 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, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles (one or more hydrogen atoms other than hydrogen atoms) (Imidazole substituted with the group Examples thereof include tetraphenylborone salts such as tetraphenylborate.

The curing accelerator (C) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the curing accelerator (C) is used, the content of the curing accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is 100, which is the content of the thermosetting component (B). It is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass with respect to parts by mass. When the content of the curing accelerator (C) is at least the lower limit value, the effect of using the curing accelerator (C) is more remarkable. When the content of the curing accelerator (C) is not more than the above upper limit value, for example, the highly polar curing accelerator (C) is coated in the thermosetting protective film forming film under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesion interface side with the body is enhanced. As a result, the reliability of the chip with a protective film obtained by using the composite sheet for forming the protective film is further improved.

[Filler (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 (that is, the protective film) can easily adjust the thermal expansion coefficient, and this heat By optimizing the expansion coefficient for the object to be formed of the protective film, the reliability of the chip with the protective film obtained by using the composite sheet for forming the protective film is further improved. Further, when the thermosetting protective film forming film contains the filler (D), the hygroscopicity of the protective film can be reduced and the heat dissipation can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, stainless steel, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; Surface modified products; single crystal fibers of these inorganic fillers; glass fibers and the like can be mentioned.
Among these, the inorganic filler is preferably silica, alumina or stainless steel. When alumina is used, it _{becomes easier to adjust S 150} and S ₂₀₀ of the protective film, and when the protective film is required to have an insulating property, it is easier to impart the insulating property to the protective film. Become. When stainless steel is used, _{the adjustment of the protective films S 150} and S ₂₀₀ becomes particularly easy.

The average particle size of the filler (D) is not particularly limited, but is preferably 10 to 4000 nm, and more preferably 30 to 3500 nm. When the average particle size of the filler (D) is in such a range, the effect of using the filler (D) can be obtained more remarkably.
For example, the amount of filler (D) in the composition (III-1) and the thermosetting protective film forming film can be easily increased, and the adjustment _{of S 150} and S _{200 of the protective film can be made more.} In terms of facilitation, the average particle size of the filler (D) is preferably 10 to 2500 nm, more preferably 20 to 1000 nm, and even more preferably 30 to 600 nm.
On the other hand, in each case, the filler (D) having an average particle size equal to or higher than the lower limit has good handleability, so that the quality of the composition (III-1) is stable and a protective film is used. It is advantageous in that the effect of being present can be stably obtained.
In the present specification, the "average particle size" means the value _{of the particle size (D 50} ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction / scattering method unless otherwise specified. ..

The filler (D) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the filler (D) is used, the ratio of the content of the filler (D) to the total content of all the components other than the solvent in the composition (III-1) (that is, for forming a thermosetting protective film). The ratio of the content of the filler (D) to the total mass of the thermosetting protective film forming film in the film) is preferably 15 to 75% by mass, more preferably 18 to 70% by mass. Preferably, it may be, for example, 45 to 70% by mass, 50 to 70% by mass, and 60 to 70% by mass. When the ratio is in such a range, the coefficient of thermal expansion of the thermosetting protective film forming film and its cured product (that is, the protective film) can be adjusted, and the protective films S ₁₅₀ and S ₂₀₀ can be adjusted. But it will be easier.

[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, it is possible to improve the adhesiveness and adhesion of the thermosetting protective film forming film to the adherend. it can. Further, by using the coupling agent (E), the cured product of the thermosetting protective film forming film has improved water resistance without impairing heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional groups of the polymer component (A), the thermosetting component (B) and the like, and is preferably a silane coupling agent. More preferred.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-. (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.

The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the 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 the polymer component (A) and the thermosetting component. The total content of (B) is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and 0.1 to 2 parts by mass with respect to 100 parts by mass. Is particularly preferable. When the content of the coupling agent (E) is equal to or higher than the lower limit, the dispersibility of the filler (D) in the resin is improved and the thermosetting protective film forming film is adhered to the adherend. The effect of using the coupling agent (E), such as improvement of the property, can be obtained more remarkably. Further, when the content of the coupling agent (E) is not more than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (F)]
As the polymer component (A), a polymer component (A) having a vinyl group capable of binding to another compound, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, an isocyanate group, or the like, such as the above-mentioned acrylic resin, is used. When used, the composition (III-1) and the thermosetting protective film-forming film may contain a cross-linking agent (F). The cross-linking agent (F) is a component for bonding the functional group in the polymer component (A) with another compound to cross-link, and by cross-linking in this way, a film for forming a thermosetting protective film. The initial adhesive force and cohesive force of the

Examples of the cross-linking agent (F) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) and the like. Can be mentioned.

When an acrylic resin or the like having the above-mentioned functional group is used as the polymer component (A), the composition (III-1) and the film for forming a thermosetting protective film can be used as a cross-linking agent (F) by heating. It may contain a cross-linking agent that reacts with a functional group. Examples of the cross-linking agent that reacts with the functional group by heating include a blocked isocyanate compound in which the isocyanate group of the organic polyvalent isocyanate compound is blocked, a polyfunctional compound having an ester exchange reactivity, and the like.

The cross-linking agent (F) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the cross-linking agent (F) is used, the content of the cross-linking agent (F) in the composition (III-1) is 0.01 to 20 mass by mass with respect to 100 parts by mass of the content of the polymer component (A). It is preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (F) is at least the lower limit value, the effect of using the cross-linking agent (F) is more remarkable. Further, when the content of the cross-linking agent (F) is not more than the upper limit value, the excessive use of the cross-linking 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 thermosetting protective film forming film contains an energy ray-curable resin (G), its characteristics can be changed by irradiation with energy rays.

The energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth) acryloyl group are preferable.

Examples of the acrylate-based compound include trimethylolpropantri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (dipentaerythritol monohydroxypenta). Chain aliphatic skeleton-containing (meth) acrylates such as meta) acrylates, dipentaerythritol hexa (meth) acrylates, 1,4-butylene glycol di (meth) acrylates, and 1,6-hexanediol di (meth) acrylates; Cyclic aliphatic skeleton-containing (meth) acrylate such as cyclopentanyldi (meth) acrylate; Polyalkylene glycol (meth) acrylate such as polyethylene glycol di (meth) acrylate; Oligoester (meth) acrylate; Urethane (meth) acrylate oligomer ; Epoxy-modified (meth) acrylate; polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; itaconic acid oligomer and the like.

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

The energy ray-curable compound used for the polymerization may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio 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, two or more types, or two types. In the above cases, their combinations and ratios can be arbitrarily selected.

When the energy ray-curable resin (G) is used, the ratio of the content of the energy ray-curable resin (G) to the total mass of the composition (III-1) in the composition (III-1) is 1 to 1. It is preferably 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by 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), light is used to efficiently proceed with the polymerization reaction of the energy ray-curable resin (G). It may contain a polymerization initiator (H).

Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal. Benzoin compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1- (4) -(4- (2-Hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one and other acetophenone compounds; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2, Acylphosphine oxide compounds such as 4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone; azobisisobutyro Azo compounds such as nitriles; titanocene compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy -2-Methyl-1- [4- (1-methylvinyl) phenyl] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone can be mentioned.
Further, as the photopolymerization initiator (H), for example, a photosensitizer such as amine can 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 kind, two or more kinds, or two or more kinds. If, the combination and ratio thereof can be arbitrarily selected.

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

[General-purpose additive (J)]
The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) as long as the effects of the present invention are not impaired.
The general-purpose additive (J) may be a known one, and may be arbitrarily selected depending on the intended purpose, and is not particularly limited, but preferred ones are, for example, plasticizers, antistatic agents, antioxidants, gettering agents, and the like. Examples include an ultraviolet absorber and an antistatic agent.

The general-purpose additive (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.
The content of the composition (III-1) and the general-purpose additive (J) of the film for forming a thermosetting protective film is not particularly limited and may be appropriately selected depending on the intended purpose.

[solvent]
The composition (III-1) preferably further contains a solvent. The solvent-containing composition (III-1) has good handleability.
The solvent is not particularly limited, but preferred ones are, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples thereof include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the composition (III-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

Among the solvents contained in the composition (III-1), more preferable ones include, for example, methyl ethyl ketone, toluene, ethyl acetate and the like from the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly. Be done.

The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected depending on, for example, the type of component other than the solvent.

<Manufacturing method of composition for forming a thermosetting protective film>
A composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending each component for forming the composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◎ Energy ray-curable protective film forming film When the energy ray-curable protective film forming film is energy-ray-cured to form a protective film, the curing conditions are such that the protective film fully exerts its function. The degree is not particularly limited, and it may be appropriately selected depending on the type of the energy ray-curable protective film forming film.
For example, the illuminance of the energy ray at the time of energy ray curing of the energy ray curable protective film forming film is preferably ^{60 to 320 mW / cm 2.} The amount of light of the energy rays at the time of curing is preferably ^{100 to 1000 mJ / cm 2.}

Examples of the film for forming an energy ray-curable protective film include those containing an energy ray-curable component (a) and a light absorber, and the energy ray-curable component (a), a light absorber and a filler are used. Those containing are preferable.
In the energy ray-curable protective film forming film, the energy ray-curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably uncured and has adhesiveness.

<Composition for forming an energy ray-curable protective film (IV-1)>
As a preferable composition for forming an energy ray-curable protective film, for example, the composition for forming an energy ray-curable protective film (IV-1) containing the energy ray-curable component (a) and a light absorber (the present specification). In the book, it may be simply abbreviated as "composition (IV-1)") and the like.

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and imparts film-forming property, flexibility, etc. to the energy ray-curable protective film forming film, and protects the film after curing. It is also a component for forming a film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000, and an energy ray-curable group having a molecular weight of 100 to 80,000. The compound (a2) can be mentioned. The polymer (a1) may be at least partially crosslinked by a crosslinking agent or may not be crosslinked.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000)
Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and the above. Examples thereof include an acrylic resin (a1-1) formed by reacting with a group that reacts with a functional group and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond. ..

Examples of the functional group capable of reacting with a group of another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom. Group), epoxy group and the like. However, in terms of preventing corrosion of circuits such as wafers and chips, the functional group is preferably a group other than a carboxy group.
Among these, the functional group is preferably a hydroxyl group.

-Acrylic polymer having a functional group (a11)
Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerizing the acrylic monomer having the functional group and the acrylic monomer having no functional group. In addition to the monomer, a monomer other than the 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 can be adopted as the polymerization method.

Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxy 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). Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Saturated alcohol (unsaturated alcohol having no (meth) acrylic skeleton) and the like can 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; fumaric acid, itaconic acid, maleic acid, and citracon. Ethylene unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like. Be done.

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

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one kind, may be two or more kinds, and when there are two or more kinds, those acrylic monomers. The combination and ratio can be selected arbitrarily.

Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n (meth) acrylate. -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ( 2-Ethylhexyl acrylate, (meth) isooctyl acrylate, n-octyl acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Undecyl acrylate, dodecyl (meth) acrylate (lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, (meth) ) Hexadecyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate) and other alkyl groups constituting the alkyl ester have 1 carbon number. Examples thereof include (meth) acrylic acid alkyl ester having a chain structure of -18.

Examples of the acrylic monomer having no functional group include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid ester having an aromatic group, including (meth) acrylic acid aryl ester such as phenyl (meth) acrylic acid; non-crosslinkable (meth) acrylamide and Derivatives thereof; (meth) acrylic acid ester having a non-crosslinkable tertiary amino group such as (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl and the like can also be mentioned. ..

The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be only one kind, may be two or more kinds, and if there are two or more kinds, they may be used. The combination and ratio of are arbitrarily selectable.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
The non-acrylic monomer constituting the acrylic polymer (a11) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof are It can be selected arbitrarily.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having a functional group to the total amount of the structural unit constituting the acrylic polymer (a11) is 0.1 to 50 mass by mass. %, More preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. When the ratio is in such a range, the energy 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 linear curable group can adjust the degree of curing of the protective film to a preferable range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be of only one type, of two or more types, and when there are two or more types, those. The combination and ratio can be selected arbitrarily.

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

-Energy ray curable compound (a12)
The energy ray-curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferable, and those having an isocyanate group as the group are more preferable. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group easily 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 contained in one molecule of the energy ray-curable compound (a12) is not particularly limited, and for example, in consideration of physical properties such as shrinkage rate required for the target protective film. Can be selected as appropriate.
For example, the energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably 1 to 3 groups.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl). Ethyl isocyanate;
Acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate;
Examples thereof include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and a hydroxyethyl (meth) acrylate.
Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be of only one type, may be of two or more types, and when there are two or more types, they may be used. The combination and ratio of are arbitrarily selectable.

In the acrylic resin (a1-1), the content of the energy ray-curable group derived from the energy ray-curable compound (a12) is relative to the content of the functional group derived from the acrylic polymer (a11). The ratio of the above is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is in such a range, the adhesive force of the cured product of the energy ray-curable protective film forming film becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%. When the energy ray-curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 20,000, more preferably 300,000 to 1,500,000.
Here, the "weight average molecular weight" is as described above.

The polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one kind, two or more kinds, or two or more kinds. If, the combination and ratio thereof can be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred ones are (meth). ) Acryloyl group, vinyl group and the like can be mentioned.

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

Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4. -((Meta) acryloxipolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxidiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloyloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol di (meth) acrylate, 1 , 10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2,2-bis [4-((Meta) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane, etc. Bifunctional (meth) acrylate;
Tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa ( Polyfunctional (meth) acrylates such as meta) acrylates;
Examples thereof include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

Among the compounds (a2), the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group are described in, for example, paragraph 0043 of "Japanese Patent Laid-Open No. 2013-194102". Can be used. Such a resin also corresponds to a resin constituting a thermosetting component described later, but is treated as the compound (a2) in the composition (IV-1).

The weight average molecular weight of the compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.

The compound (a2) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

[Polymer without energy ray-curable group (b)]
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), the polymer does not further have an energy ray-curable group. (B) is also preferably contained.
The polymer (b) may be at least partially crosslinked by a crosslinking agent or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, and an acrylic urethane resin.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").

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

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

As the (meth) acrylic acid alkyl ester, for example, the acrylic monomer having no functional group (alkyl group constituting the alkyl ester, which constitutes the acrylic polymer (a11) described above, has the number of carbon atoms. (Meta) acrylic acid alkyl ester, etc., which has a chain structure of 1 to 18).

Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl and (meth) acrylic acid dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
Examples thereof include (meth) acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester.

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

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

As the polymer (b) having no energy ray-curable group, which is at least partially crosslinked by a cross-linking agent, for example, a polymer (b) in which the reactive functional group in the polymer (b) has reacted with the cross-linking agent is used. Can be mentioned.
The reactive functional group may be appropriately selected depending on the type of the cross-linking agent and the like, and is not particularly limited. For example, when the cross-linking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, an amino group and the like, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the cross-linking agent is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group and the like, and among these, a carboxy group having high reactivity with an epoxy group is preferable. .. However, from the viewpoint of preventing corrosion of the circuit of the wafer or chip, the reactive functional group is preferably a group other than the carboxy group.

Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer listed as the monomers constituting the acrylic polymer (b-1) having the reactive functional group. It may be used. 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, and in addition to this, the above-mentioned acrylic. Examples of the based monomer and the non-acrylic monomer obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the reactive functional group can be mentioned.

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

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 1000 to 2000000 from the viewpoint of improving the film-forming property of the composition (IV-1). More preferably, it is 100,000 to 1500,000. Here, the "weight average molecular weight" is as described above.

The polymer (b) having no energy ray-curable group contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one kind, or two or more kinds. There may be two or more kinds, and the combination and ratio 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). When the composition (IV-1) contains the compound (a2), it preferably also contains a polymer (b) having no energy ray-curable group. In this case, the composition (a1) is further contained. It is also preferable to contain. Further, the composition (IV-1) does not contain the compound (a2), and may contain both the polymer (a1) and the polymer (b) having no energy ray-curable group. ..

When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the composition (IV-1) is described as described above. The content of the compound (a2) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. , 30 to 350 parts by mass, more preferably.

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of the components other than the solvent (that is, , 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 energy ray-curable protective film forming film). , 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. When the ratio of the content of the energy ray-curable component is in such a range, the energy ray-curable property of the energy ray-curable protective film forming film becomes better.

[Light absorber]
The light absorber is a component that facilitates the temperature rise of the protective film by absorbing light in a state of being present in the protective film.
Since the composition (IV-1) and the energy ray-curable protective film forming film contain a light absorber, the X _max of the protective film can be increased, and Z ₁₅₀ and Z ₂₀₀ can be increased. It will be easier.

The light absorber contained in the composition (IV-1) and the energy ray-curable protective film forming film is the light contained in the composition (III-1) and the thermosetting protective film forming film described above. Same as absorbent (I).

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

For example, the light absorber contained in the composition (IV-1) and the energy ray-curable protective film forming film preferably can absorb either one or both of visible light and infrared rays.

The light absorber contained in the composition (IV-1) and the energy ray-curable protective film forming film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected. For example, the composition (IV-1) and the film for forming an energy ray-curable protective film may contain one or more organic pigments or only one inorganic pigment as a light absorber. Alternatively, it may contain two or more kinds, or may contain one kind or two or more kinds of both an organic pigment and an inorganic pigment.

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

When the composition (IV-1) and the film for forming an energy ray-curable protective film contain an inorganic pigment as a light absorber, it preferably contains a carbon material, and both the carbon material and the organic dye. Is more preferable.

In the composition (IV-1), the ratio of the content of the light absorber to the total content of all the components other than the solvent (that is, the formation of the energy ray-curable protective film in the film for forming the energy ray-curable protective film). The ratio of the content of the light absorber to the total mass of the film for use) may be 0.1 to 20% by mass. When the ratio is at least the lower limit value, the effect of using the light absorber can be obtained more remarkably. When the ratio is not more than the upper limit value, excessive use of the light absorber is suppressed.

The composition (IV-1) and the film for forming an energy ray-curable protective film are composed of the energy ray-curable component (a), the polymer (b), and the light absorber, depending on the purpose. It may contain one or more selected from the group consisting of thermosetting components, fillers, coupling agents, cross-linking agents, photopolymerization initiators and general-purpose additives, which do not fall under any of the above.

The thermosetting component, filler, coupling agent, cross-linking agent, photopolymerization initiator and general-purpose additive in the composition (IV-1) are the thermosetting components in the composition (III-1), respectively. The same as B), filler (D), coupling agent (E), cross-linking agent (F), photopolymerization initiator (H) and general-purpose additive (J) can be mentioned.

For example, when the composition (IV-1) contains a thermosetting component, the energy ray-curable protective film forming film formed by using such a composition (IV-1) is heated. The adhesive force to the adherend is improved, and the strength of the protective film formed from the energy ray-curable protective film forming film is also improved.

In the composition (IV-1), one type of the thermosetting component, the filler, the coupling agent, the cross-linking agent, the photopolymerization initiator and the general-purpose additive may be used alone or two types, respectively. The above may be used in combination, and when two or more types are used in combination, their combinations and ratios can be arbitrarily selected.

The contents of the thermosetting component, filler, coupling agent, cross-linking agent, photopolymerization initiator and general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the intended purpose and are not particularly limited. ..

The composition (IV-1) is preferably further containing a solvent because its handleability is improved by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The solvent contained in the composition (IV-1) may be only one kind or two or more kinds.
The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected depending on, for example, the type of component other than the solvent.

<Manufacturing method of composition for forming energy ray-curable protective film>
A composition for forming an energy ray-curable protective film such as the composition (IV-1) can be obtained by blending each component for forming the composition.
The energy ray-curable protective film-forming composition can be produced, for example, by the same method as in the case of the thermosetting protective film-forming composition described above, except that the types of compounding components are different.

◎ Film for forming a non-curable protective film Preferred film for forming a non-curable protective film includes, for example, a film containing a thermoplastic resin, a light absorber and a filler.

<Composition for forming a non-curable protective film (V-1)>
As a preferable non-curable protective film-forming composition, for example, the non-curable protective film-forming composition (V-1) containing the thermoplastic resin, a light absorber and a filler (in the present specification, It may be simply abbreviated as "composition (V-1)") and the like.

[Thermoplastic resin]
The thermoplastic resin is not particularly limited.
More specifically, as the thermoplastic resin, for example, the acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene and the like mentioned as the components contained in the above composition (III-1) are cured. Examples include those similar to non-sexual resins.

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

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

[Light absorber]
The light absorber is a component that facilitates the temperature rise of the protective film by absorbing light in a state of being present in the protective film.
Since the composition (V-1) and the film for forming a non-curable protective film contain a light absorber, the X _max of the protective film becomes larger, and Z ₁₅₀ and Z ₂₀₀ can be made larger. It will be easy.

The light absorber contained in the composition (V-1) and the non-curable protective film forming film is the light absorption contained in the composition (III-1) and the thermosetting protective film forming film described above. Same as agent (I).

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

For example, the light absorber contained in the composition (V-1) and the film for forming a non-curable protective film preferably can absorb either one or both of visible light and infrared rays.

The light absorber contained in the composition (V-1) and the film for forming a non-curable protective film may be only one kind, two or more kinds, or two or more kinds, when there are two or more kinds. The combination and ratio thereof can be arbitrarily selected. For example, the composition (V-1) and the film for forming a non-curable protective film may contain one or more organic pigments as a light absorber, or one or more inorganic pigments. It may contain two or more kinds, or may contain one kind or two or more kinds of both organic pigments and inorganic pigments.

The composition (V-1) and the film for forming a non-curable protective film preferably contain two or more kinds of light absorbers capable of absorbing either one or both of visible light and infrared rays, and 2 to 7 kinds thereof. It is more preferable to contain it.

When the composition (V-1) and the film for forming a non-curable protective film contain an inorganic pigment as a light absorber, it preferably contains a carbon material, and may contain both the carbon material and the organic dye. More preferred.

In the composition (V-1), the ratio of the content of the light absorber to the total content of all the components other than the solvent (that is, the film for forming a non-curable protective film in the film for forming a non-curable protective film). The ratio of the content of the light absorber to the total mass of the light absorber) may be 0.1 to 20% by mass. When the ratio is at least the lower limit value, the effect of using the light absorber can be obtained more remarkably. When the ratio is not more than the upper limit value, excessive use of the light absorber is suppressed.

[Filler]
The non-curable protective film forming film containing the filler has the same effect as the thermosetting protective film forming film containing the filler (D).

The filler contained in the composition (V-1) and the non-curable protective film forming film is the same as the filler (D) contained in the composition (III-1) and the thermosetting protective film forming film. Things can be mentioned.

The filler contained in the composition (V-1) and the film for forming a non-curable protective film may be only one kind, may be two or more kinds, and when two or more kinds, they may be used. The combination and ratio of are arbitrarily selectable.

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

The composition (V-1) may contain other components that do not fall under any of the thermoplastic resin, the light absorber, and the filler, depending on the purpose.
The other components are not particularly limited and can be arbitrarily selected depending on the intended purpose.

In the composition (V-1), one of the other components may be used alone, two or more of them may be used in combination, and when two or more of them are used in combination, the combination and ratio thereof shall be different. It can be selected arbitrarily.

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

The composition (V-1) is preferably further containing a solvent because its handleability is improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the above-mentioned composition (III-1).
The solvent contained in the composition (V-1) may be only one kind or two or more kinds.
The content of the solvent in the composition (V-1) is not particularly limited, and may be appropriately selected depending on, for example, the type of component other than the solvent.

<Manufacturing method of non-curable protective film forming composition>
A non-curable protective film forming composition such as the composition (V-1) can be obtained by blending each component for forming the composition.
The non-curable protective film-forming composition can be produced, for example, by the same method as in the case of the thermosetting protective film-forming composition described above, except that the types of compounding components are different.

FIG. 1 is a cross-sectional view schematically showing an example of a protective film forming film according to an embodiment of the present invention. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio of each component is the same as the actual one. Is not always the case.

The protective film forming film 13 shown here includes a first release film 151 on one surface (sometimes referred to as a “first surface” in the present specification) 13a, and the first surface 13a and the film 13 are provided with the first release film 151. Provided a second release film 152 on the other side (sometimes referred to as the "second side" in the present specification) 13b on the opposite side.
Such a protective film forming film 13 is suitable for storage as, for example, in the form of a roll.

The protective film forming film 13 has the above-mentioned characteristics.
The protective film forming film 13 can be formed by using the above-mentioned 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, or are different from each other, for example, the release forces required for peeling from the film-like adhesive 13 are different from each other. May be good.

In the protective film forming film 13 shown in FIG. 1, either the first release film 151 or the second release film 152 is removed, and the resulting exposed surface becomes a surface to be attached to the back surface of the wafer (not shown). .. Then, the other of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface is a support sheet or a dicing sheet described later (sometimes referred to as a "dicing tape" in the present specification). It becomes the sticking surface of. For example, when the first surface 13a is the attachment surface to the back surface of the wafer, the second surface 13b is the attachment surface of the support sheet or the dicing sheet.

FIG. 1 shows an example in which the release film is provided on both sides (first surface 13a, second surface 13b) of the protective film forming film 13, but the release film is the protective film forming film 13. It may be provided only on one of the surfaces, that is, only the first surface 13a or only the second surface 13b.

The protective film forming film of the present embodiment can be attached to the back surface of the wafer without being used in combination with the support sheet described later. In that case, a release film may be provided on the surface opposite to the surface on which the protective film forming film is attached to the wafer, and this release film may be removed at an appropriate timing. A dicing sheet is attached to the exposed surface of the protective film forming film after the release film is removed, and the protective film is formed by dicing, that is, dividing the wafer and cutting the protective film forming film or the protective film. Attached chips can be manufactured.

On the other hand, the protective film forming film of the present embodiment can be used in combination with a support sheet described later to form a protective film forming composite sheet capable of both forming the protective film and dicing. Hereinafter, such a composite sheet for forming a protective film will be described.

Protective Film Forming Composite Sheet The protective film forming composite sheet according to the embodiment of the present invention includes a support sheet and a protective film forming film provided on one surface of the support sheet. The protective film forming film is the protective film forming film according to the above-described embodiment of the present invention.

The composite sheet for forming a protective film of the present embodiment is provided with the film for forming a protective film, so that, as a chip with a protective film, the protruding electrodes in the composite sheet and the connection pad on the circuit board are electrically connected. The connection strength can be further strengthened in the manufacturing process of the substrate device.

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

Hereinafter, each layer constituting the protective film forming composite sheet will be described in detail.

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

The support sheet may be transparent, opaque, or colored depending on the purpose.
For example, when the protective film forming film has energy ray curability, the support sheet preferably allows energy rays to pass through.

Examples of the support sheet include a base material and a pressure-sensitive adhesive layer provided on one surface of the base material; a base material only; and the like. When the support sheet includes the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is arranged between the base material and the protective film-forming film in the protective film-forming composite sheet.

When a support sheet provided with a base material and an adhesive layer is used, the adhesive force or adhesiveness between the support sheet and the protective film-forming film can be easily adjusted in the protective film-forming composite sheet.
When a support 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 a support sheet with reference to the drawings.

FIG. 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.
In the drawings after FIG. 2, the same components as those shown in the already explained figures are designated by the same reference numerals as in the case of the already explained figures, and detailed description thereof will be omitted.
The protective film forming composite sheet 101 shown here is a protective film provided on the support sheet 10 and one surface of the support sheet 10 (sometimes referred to as a "first surface" in the present specification) 10a. It is configured to include a forming film 13.
The support sheet 10 includes a base material 11 and an adhesive layer 12 provided on one surface (that is, the first surface) 11a of the base material 11. In the protective film forming composite sheet 101, the pressure-sensitive adhesive layer 12 is arranged between the base material 11 and the protective film forming film 13.
That is, the protective film-forming composite sheet 101 is configured by laminating the base material 11, the pressure-sensitive adhesive layer 12, and the protective film-forming film 13 in this order in the thickness direction.
The surface (sometimes referred to as the "first surface" in the present specification) 10a of the support sheet 10 on the protective film forming film 13 side is the surface of the pressure-sensitive adhesive layer 12 opposite to the base material 11 side (the surface is opposite to the base material 11 side). In this specification, it is the same as 12a) (sometimes referred to as "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 adhesive layer 12, and is different from the adhesive layer 12 side of the protective film forming film 13. The adhesive layer 16 for jigs is laminated on a part of the opposite surface (sometimes referred to as the "first surface" in the present specification) 13a, that is, in a region near the peripheral edge portion. Further, in the first surface 13a of the protective film forming film 13, the region where the jig adhesive layer 16 is not laminated and the side opposite to the protective film forming film 13 side of the jig adhesive layer 16. The release film 15 is laminated on the surface (sometimes referred to as the "first surface" in the present specification) 16a.

Not limited to the case of the protective film forming composite sheet 101, in the protective film forming composite sheet of the present embodiment, the release film (for example, the release film 15 shown in FIG. 1) has an arbitrary configuration, and the present embodiment has an arbitrary configuration. The composite sheet for forming a protective film may or may not include a release film.

In the protective film forming composite sheet 101, 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 release film 15 is in contact (laminated) with the side surface 16c of the jig adhesive layer 16, but the release film 15 is not in contact with the side surface 16c. There is also. Further, here, the state in which the release film 15 is in contact (laminated) with the region near the jig adhesive layer 16 in the first surface 13a of the protective film forming film 13 is shown. The release film 15 may not be in contact with the region.
Further, the boundary between the first surface 16a and the side surface 16c of the jig adhesive layer 16 may not be clearly distinguishable.
The above points are the same for the composite sheet for forming a protective film of another embodiment provided with the adhesive layer for jigs.

The jig adhesive layer 16 is used to fix the protective film forming composite sheet 101 to a jig such as a ring frame.
The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. It may have a structure.

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

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

FIG. 3 is a cross-sectional view schematically showing another example of the protective film forming composite sheet according to the embodiment of the present invention.
The protective film-forming composite sheet 102 shown here has a different shape and size of the protective film-forming film, and the adhesive layer for jigs is not the first surface of the protective film-forming film but the first adhesive layer. It is the same as the protective film forming composite sheet 101 shown in FIG. 1 except that it is laminated on the surface.

More specifically, in the protective film forming composite sheet 102, the protective film forming film 23 is a part of a region of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the width direction of the pressure-sensitive adhesive layer 12 (FIG. 3). It is laminated in the region on the central side in the left-right direction). Further, the jig adhesive layer 16 is laminated on the first surface 12a of the pressure-sensitive adhesive layer 12 in the region where the protective film forming film 23 is not laminated, that is, in the region near the peripheral edge portion. Then, the surface of the protective film forming film 23 opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in the present specification) 23a and the jig adhesive layer 16 are the first. The release film 15 is laminated on one surface 16a.

FIG. 4 is a cross-sectional view schematically showing still another example of the protective film forming composite sheet according to the 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.

FIG. 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 in place of the support sheet 10.
The support sheet 20 is composed of only the base material 11.
That is, the protective film forming composite sheet 104 is formed by laminating the base material 11 and the protective film forming film 13 in the thickness direction thereof.
The surface (sometimes referred to as “first surface” in the present specification) 20a on the protective film forming film 13 side of the support sheet 20 is the same as the first surface 11a of the base material 11.
The base material 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 the one shown in FIGS. 1 to 5, and a part of the configuration shown in FIGS. 1 to 5 is changed within a range not impairing the effect of the present invention. Alternatively, it may be deleted, or may have other configurations added to those described above. More specifically, it is as follows.

Up to this point, only the protective film-forming composite sheet 104 shown in FIG. 5 is shown as the protective film-forming composite sheet including the support sheet made of only the base material, but the support sheet made of only the base material is provided. Examples of the protective film-forming composite sheet include the protective film-forming composite sheet 102 shown in FIG. 3 and the protective film-forming composite sheet 103 shown in FIG. 4 which does not have the pressure-sensitive adhesive layer 12. .. However, this is an example of another composite sheet for forming a protective film having a support sheet composed of only a base material.

Up to this point, as for the protective film forming composite sheet that does not have the jig adhesive layer, only the protective film forming composite sheet 103 shown in FIG. 4 is shown, but the jig adhesive layer is provided. As a protective film-forming composite sheet, for example, the protective film-forming composite sheet 101 shown in FIG. 2 does not have the adhesive layer 16 for a jig; in the protective film-forming composite sheet 104 shown in FIG. , Which does not have the adhesive layer 16 for jigs; However, this is an example of another composite sheet for forming a protective film that does not have an adhesive layer for jigs.

Up to this point, the base material, the pressure-sensitive adhesive layer, the protective film-forming film and the release film have been shown as the layers constituting the protective film-forming composite sheet, but other layers that do not correspond to any of these are used. A composite sheet for forming a protective film may be provided.
The type of the other layer is not particularly limited and can be arbitrarily selected depending on the intended purpose.
The arrangement position, shape, size, etc. of the other layers can be arbitrarily selected according to the type, and are not particularly limited.

The other layer is arranged between the support sheet and the protective film forming film, and is used for forming a protective film, for example, by adjusting the peelability of the protective film forming film or a cured product thereof from the supporting sheet. Examples thereof include an intermediate layer that imparts some property to the composite sheet.
However, this is an example of another protective film forming composite sheet 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 support sheet will be described in more detail.

○ Base material The base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); other than polyethylenes such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyethylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as monomer) (Copolymers obtained using); Vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefins; Polyethylene terephthalate, polyethylene Polymers such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, all aromatic polyesters in which all constituent units have aromatic cyclic groups; co-polymers of two or more of the above polymers. Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; polyether ketones and the like.
Further, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.
Further, as the resin, for example, a crosslinked resin in which one or more of the resins exemplified above are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.

The resin constituting the base material may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

The thickness of the base material is preferably 50 to 300 μm, more preferably 60 to 100 μm. When the thickness of the base material is within such a range, the flexibility of the composite sheet for forming the protective film and the adhesiveness to the wafer are further improved.
Here, the "thickness of the base material" means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.

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

The base material may be transparent, opaque, colored depending on the purpose, or another layer may be vapor-deposited.
For example, when the protective film forming film has energy ray curability, the base material preferably transmits energy rays.

The base material is subjected to a sandblasting treatment, a solvent treatment or the like to make the base material uneven in order to adjust the adhesiveness with a layer provided on the base material (for example, an adhesive layer, a protective film forming film, or the other layer). Oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment; lipophilic treatment; hydrophilic treatment and the like may be applied to the surface. Further, the surface of the base material may be primed.

The base material may have adhesiveness on at least one surface by containing a specific range of components (for example, resin or the like).

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

○ Adhesive layer The adhesive layer is in the form of a sheet or a film and contains an adhesive.
Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins.

In the present specification, the "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only the resin itself having adhesiveness, but also a resin showing adhesiveness when used in combination with other components such as additives, and adhesiveness due to the presence of a trigger such as heat or water. Also included are resins and the like.

The pressure-sensitive adhesive layer may be composed of one layer (single layer), may be composed 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. The combination of these plurality of layers is not particularly limited.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the sum of all the layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

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

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

The 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.

When the pressure-sensitive adhesive layer is provided on the base material, for example, the pressure-sensitive adhesive layer may be laminated on the base material by applying the pressure-sensitive adhesive composition on the base material and drying it if necessary. When the pressure-sensitive adhesive layer is provided on the base material, for example, the pressure-sensitive adhesive composition is applied onto the release film and dried as necessary to form the pressure-sensitive adhesive layer on the release film. The pressure-sensitive adhesive layer may be laminated on the base material by adhering the exposed surface of the pressure-sensitive adhesive layer to one surface of the base material. In this case, the release film may be removed at any timing of the manufacturing process or the use process of the protective film forming composite sheet.

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 pressure-sensitive adhesive composition contains a solvent described later, it is preferable to heat-dry it. The pressure-sensitive adhesive composition containing the solvent is preferably heat-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 includes, for example, a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, "sticky resin (I-)". 1a) ”) and an energy ray-curable compound are contained in the pressure-sensitive adhesive composition (I-1); on the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). A pressure-sensitive adhesive composition (I-) containing an energy ray-curable pressure-sensitive adhesive resin (I-2a) into which an unsaturated group has been introduced (hereinafter, may be abbreviated as "sticky resin (I-2a)"). 2); Examples thereof include a pressure-sensitive adhesive composition (I-3) containing the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.

When the pressure-sensitive adhesive layer is non-energy ray-curable, the non-energy ray-curable pressure-sensitive adhesive composition includes, for example, the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). (I-4) and the like can be mentioned.

[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, these pressure-sensitive adhesive compositions are included). The adhesive resin (I-1a) in the "adhesive compositions (I-1) to (I-4)") is preferably an acrylic resin.

Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from (meth) acrylic acid alkyl ester.
Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferable.

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester.
As the functional group-containing monomer, for example, the functional group may be a starting point of cross-linking by reacting with a cross-linking agent described later, or the functional group may react with an unsaturated group in an unsaturated group-containing compound described later. Then, there is one that enables the introduction of an unsaturated group into the side chain of the acrylic polymer.

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

The acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer.
The other monomer is not particularly limited as long as it can be copolymerized with a (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

In the pressure-sensitive adhesive compositions (I-1) to (I-4), the structural unit of the acrylic resin such as the acrylic polymer may be only one type, two or more types, or two or more types. If, the combination and ratio thereof can be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass 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 only one type, two or more types, or two or more types. If so, their combinations and ratios can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4), the pressure-sensitive resin (I) with respect to the total mass of the pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4). The ratio of the content of -1a) is preferably 5 to 99% by mass.

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

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group. It is a compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. And so on.

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

The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-2) or (I-3) may be only one type, two or more types, or two or more types. If, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2) or (I-3), the ratio of the content of the pressure-sensitive resin (I-2a) to the total mass of the pressure-sensitive adhesive composition (I-2) or (I-3). Is preferably 5 to 99% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound in the pressure-sensitive adhesive compositions (I-1) and (I-3) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. Be done.

Among the energy ray-curable compounds, examples of the monomer include trimethylpropantri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4. Polyvalent (meth) acrylates such as −butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) Acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerizing the monomers exemplified above.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) or (I-3) may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content 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 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). Is preferable.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition ( I-1) or (I-4) preferably further contains a cross-linking agent.
Further, when the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), the pressure-sensitive adhesive composition is used. The substance (I-2) or (I-3) may further contain a cross-linking agent.

The cross-linking agent reacts with the functional group, for example, to cross-link the adhesive resins (I-1a) or the adhesive resins (I-2a).
Examples of the cross-linking agent include isocyanate-based cross-linking agents such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates (cross-linking agents having an isocyanate group); and epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agents). Cross-linking agent having a glycidyl group); Isocyanate-based cross-linking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (cross-linking agent having an aziridinyl group); Metal chelate-based cross-linking agent such as aluminum chelate (metal) Crosslinking agent having a chelate structure); Isocyanurate-based crosslinking agent (crosslinking agent having an isocyanurate skeleton) and the like can be mentioned.

The cross-linking agent contained in the pressure-sensitive adhesive composition (I-1), (I-2) or (I-4) may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-1) or (I-4), the content of the cross-linking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). Is preferable.
In the pressure-sensitive adhesive composition (I-2) or (I-3), the content of the cross-linking agent is 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). Is preferable.

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

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone and 2-hydroxy. Acetphenone compounds such as -2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone; azo Azo compounds such as bisisobutyronitrile; titanosen compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane 2-Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; Examples thereof include quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Further, as the photopolymerization initiator, for example, a photosensitizer such as amine can be used.

The photopolymerization initiators contained in the pressure-sensitive adhesive compositions (I-1) to (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

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

[Other additives]
The pressure-sensitive adhesive compositions (I-1) to (I-4) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additives include antioxidants, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. , Known additives such as reaction retarders and cross-linking accelerators (catalysts).
The reaction delaying agents are, for example, the pressure-sensitive adhesive compositions (I-1) to (I-1) to be stored due to the action of the catalyst mixed in the pressure-sensitive adhesive compositions (I-1) to (I-4). In I-4), it is a component that suppresses the progress of an unintended cross-linking reaction. Examples of the reaction retarder include those that form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

The other additives contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof may be It can be selected arbitrarily.

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 depending on the type thereof.

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

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

The solvent contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one type, two or more types, or a combination thereof when two or more types are used. And the ratio can be selected arbitrarily.

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.

○ Method for Producing Adhesive Composition The pressure-sensitive adhesive compositions such as the pressure-sensitive adhesive compositions (I-1) to (I-4) are adhered to the pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive. It is obtained by blending each component for constituting an agent composition.
The pressure-sensitive adhesive composition can be produced, for example, by the same method as in the case of the thermosetting protective film-forming composition described above, except that the types of compounding components are different.

◇ Method for manufacturing a composite sheet for forming a protective film The composite sheet for forming a protective film is laminated so that the above-mentioned layers have a corresponding positional relationship, and the shape of a part or all of the layers is adjusted as necessary. It can be manufactured. The method of forming each layer is as described above.

For example, when a pressure-sensitive adhesive layer is laminated on a base material when manufacturing a support sheet, the above-mentioned pressure-sensitive adhesive composition may be applied onto the base material and dried if necessary.
Further, the pressure-sensitive adhesive composition is applied onto the release film and dried as necessary to form a pressure-sensitive adhesive layer on the release film, and the exposed surface of the pressure-sensitive adhesive layer is used as one of the base materials. The pressure-sensitive adhesive layer can also be laminated on the base material by the method of bonding to the surface of the above. At this time, it is preferable that the pressure-sensitive adhesive composition is applied to the peel-treated surface of the release film.
Up to this point, the case of laminating the pressure-sensitive adhesive layer on the base material has been described as an example, but the above method can also be applied to, for example, the case of laminating an intermediate layer or the other layer on the base material.

On the other hand, for example, when a protective film-forming film is further laminated on the pressure-sensitive adhesive layer already laminated on the base material, the protective film-forming composition is applied on the pressure-sensitive adhesive layer to form a protective film. It is possible to directly form a forming film. Layers other than the protective film-forming film can also be laminated on the pressure-sensitive adhesive layer in the same manner by using the composition for forming this layer. In this way, a new layer (hereinafter, abbreviated as "second layer") is formed on any of the layers already laminated on the base material (hereinafter, abbreviated as "first layer"). When forming a continuous two-layer laminated structure (in other words, a laminated structure of the first layer and the second layer), a composition for forming the second layer is applied on the first layer. Then, a method of drying can be applied if necessary.
However, the second layer is formed in advance on the release film using the composition for forming the second layer, and the side of the formed second layer opposite to the side in contact with the release film. It is preferable to form a continuous two-layer laminated structure by laminating the exposed surface of the first layer with the exposed surface of the first layer. At this time, it is preferable that the composition is applied to the peeled surface of the peeling film. The release film may be removed if necessary after the laminated structure is formed.
Here, the case where the protective film forming film is laminated on the pressure-sensitive adhesive layer is taken as an example, but for example, when the intermediate layer or the other layer is laminated on the pressure-sensitive adhesive layer, the target laminated structure is , Can be selected arbitrarily.

As described above, all the layers other than the base material constituting the protective film forming composite sheet can be laminated in advance by forming them on the release film and laminating them on the surface of the target layer, so that they can be laminated as needed. A layer for adopting such a process may be appropriately selected to produce a composite sheet for forming a protective film.

The protective film-forming composite sheet is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, the protective film-forming film) on the opposite side of the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is applied onto the release film (preferably the release-treated surface thereof) and dried if necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface on the side opposite to the side in contact with the release film of this layer by any of the above methods. However, by leaving the release film in a bonded state without removing it, a composite sheet for forming a protective film with a release film can be obtained.

◇ Manufacturing method of chips with protective film (How to use protective film forming film and protective film forming composite sheet)
The protective film-forming film and the protective film-forming composite sheet can be used for producing the protective film-attached chip.

<< Manufacturing Method 1 >>
As a method of manufacturing a chip with a protective film by attaching the protective film forming film to a wafer without using it in combination with a support sheet, for example,
A laminate (1) or a wafer comprising a wafer and a protective film forming film provided on the back surface of the wafer through a process of attaching the protective film forming film to the back surface of the wafer, and the wafer. The first laminating step of obtaining a laminated body (1') provided with a protective film provided on the back surface of the wafer, and
Dicing on the surface of the laminated body (1) opposite to the wafer side of the protective film forming film, or on the surface of the laminated body (1') opposite to the wafer side of the protective film. The dicing sheet, the protective film forming film, and the wafer are laminated in this order in this order through the process of attaching the sheet, or the laminate (2) or the above. A second laminating step of obtaining a laminated body (2') in which the dicing sheet, the protective film, and the wafer are laminated in this order in the thickness direction.
The wafer in the laminate (2) is divided to produce a chip, and the protective film forming film is cut along the divided portion of the wafer, and the wafer is provided on the chip and the back surface of the chip. A plurality of chips with a protective film forming film provided with the cut protective film forming film, which are held on the dicing sheet to form a chip assembly with the protective film forming film. Or the wafer in the laminate (2') is divided to produce a chip, and the protective film is cut along the divided portion of the wafer to obtain the chip and the chip. A plurality of protective film-attached chips provided with the protective film after cutting provided on the back surface of the dicing sheet are held on the dicing sheet to obtain a protective film-attached chip aggregate. Cutting process and
The chip with the protective film forming film in the chip assembly with the protective film forming film or the chip with the protective film in the chip assembly with the protective film is separated from the dicing sheet and picked up. It has a chip acquisition process with a protective film to obtain a chip with a protective film,
When the protective film forming film is curable, further, after the protective film forming film is attached to the back surface of the wafer in the first laminating step, in the step of obtaining a chip with a protective film. At any stage until after the chip with the protective film forming film is picked up, the laminated body (1), the laminated body (2), the chip aggregate with the protective film forming film, or the chip with the protective film forming film. By curing the protective film-forming film inside to form a protective film, the laminate (1'), the laminate (2'), a chip aggregate with a protective film, or a chip with a protective film is produced. Examples thereof include a method for manufacturing a chip with a protective film having a curing step (referred to as “manufacturing method 1” in the present specification).

The protective film forming film used in the first laminating step of the manufacturing method 1 is the protective film forming film according to the above-described embodiment of the present invention.

In the first laminating step of the manufacturing method 1, when the protective film forming film is curable, the protective film forming film is attached to the back surface of the wafer, and then the protective film forming film after the attachment is attached. It can be cured, whereby the laminate (1') can be obtained.
On the other hand, when the protective film forming film is non-curable, the laminated body (1') is immediately obtained by attaching the protective film forming film to the back surface of the wafer.

The dicing sheet used in the second laminating step of the production method 1 may be a known one.

The curing step can be performed at any stage as long as it is after the protective film forming film is attached to the back surface of the wafer in the first laminating step. For example, the curing step is performed after obtaining the laminated body (1) in the first laminating step; between the first laminating step and the second laminating step; after obtaining the laminated body (2) in the second laminating step. Between the second laminating process and the dividing / cutting process; after obtaining the chip assembly with the protective film forming film during the dividing / cutting process; between the dividing / cutting process and the chip obtaining process with the protective film; After picking up the chip with the protective film forming film in the process of obtaining the attached chip;
When the protective film forming film is non-curable, the production method 1 does not have the curing step.

In the production method 1, the curing of the protective film forming film is thermosetting or energy ray curing at any stage. The conditions for thermosetting and the conditions for energy ray curing at this time are as described above.

The first laminating step, the second laminating step, the dividing / cutting step, the chip acquisition step with a protective film, and the curing step in the manufacturing method 1 are different from the point that the protective film forming film according to the present embodiment is used. It can be performed by the same method as in the case of the 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 attached is not particularly limited, but is preferably 20 to 600 μm, more preferably 40 to 400 μm.

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

<< Manufacturing Method 2 >>
That is, the manufacturing method 2 goes through a process of cutting the protective film forming film in the laminated body (2) and dividing the wafer along the cut portion of the protective film forming film to produce a chip. A plurality of chips with a protective film forming film provided on the back surface of the chip and the protective film forming film after cutting are held and configured on the dicing sheet. Alternatively, an aggregate of chips with a protective film-forming film is obtained, or the protective film in the laminated body (2') is cut, and the wafer is divided along the cut portion of the protective film to obtain a chip. Through the manufacturing process, a plurality of protective film-attached chips provided with the chip and the protective film after cutting provided on the back surface of the chip were held and configured on the dicing sheet. It has a cutting / dividing step of obtaining a chip assembly with a protective film.
The manufacturing method 2 is the same as the manufacturing method 1 except that it has a cutting / splitting step instead of the splitting / cutting step. That is, the manufacturing method 2 includes the first laminating step, the second laminating step, the cutting / dividing step, and the chip acquisition step with the protective film, and the protective film forming film is curable. In the case of, further, after the protective film forming film is attached to the back surface of the wafer in the first laminating step, the protective film forming film-attached chip in the protective film-forming chip acquisition step. At any stage until after pick-up, the protective film-forming film in the laminated body (1), the laminated body (2), the chip aggregate with the protective film-forming film, or the chip with the protective film-forming film is cured. It has a curing step of producing the laminated body (1'), the laminated body (2'), the chip aggregate with the protective film, or the chip with the protective film by forming the protective film.

<< Manufacturing Method 3 >>
As a method for producing a chip with a protective film, for example, the protective film forming film is used in combination with a support sheet and attached to a wafer as a protective film forming composite sheet.
The support sheet, the protective film forming film, and the wafer are laminated in this order in the thickness direction through the process of attaching the protective film forming film in the protective film forming composite sheet to the back surface of the wafer. Lamination to obtain a laminate (3) configured by being laminated, or a laminate (3') composed of a support sheet, a protective film, and a wafer laminated in this order in the thickness direction. Process and
The wafer in the laminate (3) is divided to produce a chip, and the protective film forming film is cut along the divided portion of the wafer, and the chip and the back surface of the chip are provided. A plurality of protective film-forming film-attached chips provided with the cut protective film-forming film, which are held on the support sheet to form a protective film-forming film-attached chip aggregate. Or the wafer in the laminate (3') is divided to produce a chip, and the protective film is cut along the divided portion of the wafer to obtain the chip and the chip. A plurality of protective film-attached chips provided with the protective film after cutting provided on the back surface of the support sheet are held on the support sheet to obtain a protective film-attached chip aggregate. Cutting process and
The chip with the protective film forming film in the chip assembly with the protective film forming film or the chip with the protective film in the chip assembly with the protective film is separated from the support sheet and picked up. It has a chip acquisition process with a protective film to obtain a chip with a protective film,
When the protective film forming film is curable, the protective film is further applied to the back surface of the wafer in the protective film forming composite sheet in the laminating step. At any stage after picking up the protective film-forming film-attached chip in the attached chip acquisition step, the laminate (3), the protective film-forming film-attached chip aggregate, or the protective film-forming film-attached chip A protective film having a curing step of producing the laminate (3'), a chip aggregate with a protective film, or a chip with a protective film by curing the protective film forming film inside to form a protective film. Examples thereof include a method for manufacturing a attached chip (referred to as “manufacturing method 3” in the present specification).

The protective film forming film used in the laminating step of the manufacturing method 3 is the protective film forming film according to the above-described embodiment of the present invention.

In the laminating step of the manufacturing method 3, when the protective film forming film is curable, a protective film forming composite sheet is attached to the back surface of the wafer, and then in the protective film forming composite sheet after the attachment. The protective film-forming film can be cured, whereby the laminated body (3') can be obtained.
On the other hand, when the protective film forming film is non-curable, the laminated body (3') is immediately obtained by attaching the protective film forming composite sheet to the back surface of the wafer.

The laminated body (3) obtained in the laminating step of the manufacturing method 3 is substantially the same as the laminated body (2) obtained in the second laminating step of the manufacturing method 1.
Similarly, the laminated body (3') obtained in the laminating step of the manufacturing method 3 is substantially the same as the laminated body (2') obtained in the second laminating step of the manufacturing method 1.

The curing step can be performed at any stage as long as it is after the protective film forming film in the protective film forming composite sheet is attached to the back surface of the wafer in the laminating step. For example, the curing step is performed after obtaining the laminated body (3) in the laminating step; between the laminating step and the dividing / cutting step; after obtaining the chip aggregate with the protective film forming film in the dividing / cutting step; It can be performed either between the dividing / cutting step and the protective film-attached chip acquisition step; after picking up the protective film-forming film-attached chip in the protective film-attached chip acquisition step.
When the protective film forming film is non-curable, the production method 3 does not have the curing step.

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

In the manufacturing method 3, the lamination step, the dividing / cutting step, the chip acquisition step with a protective film, and the curing step are conventional chips with a protective film except that the composite sheet 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 the manufacturing method of.
For example, the thickness of the wafer to which the composite sheet for forming the protective film is attached is not particularly limited, but is preferably 20 to 600 μm, more preferably 40 to 400 μm.

<Other processes>
The manufacturing method 1 is described in addition to the first laminating step, the second laminating step, the dividing / cutting step, the chip acquisition step with a protective film, and the curing step, as long as the effects of the present invention are not impaired. It may have other steps that do not correspond to any of the above.
Similarly, the manufacturing method 2 is other than the first laminating step, the second laminating step, the cutting / dividing step, the chip acquisition step with a protective film, and the curing step, as long as the effects of the present invention are not impaired. In addition, it may have other steps that do not correspond to any of these.
Similarly, the manufacturing method 3 can be applied to any of these steps in addition to the laminating step, the dividing / cutting step, the chip acquisition step with a protective film, and the curing step, as long as the effects of the present invention are not impaired. It may have other steps that do not apply.
In any of the production methods 1 to 3, the type of the other process and the timing at which the process is performed can be arbitrarily selected according to the purpose and are not particularly limited.

◇ Manufacturing method of substrate device After obtaining a chip with a protective film by the above-mentioned manufacturing method, the substrate device can be manufactured by the same method as the conventional manufacturing method except that the chip with the protective film is used.
As a method for manufacturing such a substrate device, for example,
The chip arrangement for arranging the protective film-attached chip on the circuit board by bringing the protruding electrode on the protective film-attached chip obtained by using the protective film-forming film into contact with the connection pad on the circuit board. Process and
By heating the chip with the protective film arranged on the circuit board using a halogen heater, the projecting electrode on the chip with the protective film is melted, and the projecting electrode is connected to the circuit board. Examples thereof include a manufacturing method including a flip chip connecting step for improving the connection strength between the pad and the pad.

In the substrate device obtained by the above-mentioned manufacturing method, by using the chip with the protective film, the electrical connection strength between the protruding electrode and the connection pad on the circuit board becomes stronger than usual. Become. Therefore, such a substrate device has high reliability.
This is because, as described above, in the flip chip connection step, the protective film in the chip with the protective film during heating absorbs a large amount of near infrared rays, and the temperature of the protective film during heating is higher than usual. This is to become. Due to the action of this protective film, which has become hotter, the protruding electrode on the chip with the protective film also becomes hotter, and as a result, the protruding electrode tends to melt, and as a result, the connection between the protruding electrode and the circuit board. The electrical connection strength between the pad and the pad becomes stronger than usual.

In the flip chip connection step, the maximum temperature reached by the protective film during heating can be set to, for example, 250 ° C or higher, 260 ° C or higher, 270 ° C or higher, or 280 ° C or higher. Is.

FIG. 6 is a cross-sectional view schematically showing a state in which the chip with a protective film and the circuit board are electrically connected in the flip chip connecting step.
Here, the state in which the chip 901 with the protective film and the circuit board 8 are electrically connected is shown.
The chip 901 with a protective film includes a chip 9 and a protective film 130'after cutting provided on the back surface 9b of the chip 9. A plurality of protruding electrodes 91 are provided on the circuit surface 9a of the chip 9.
A plurality of connection pads 81 are provided on the circuit surface 8a of the circuit board 8.
The one protruding electrode 91 on the chip 9 and the one connection pad 81 on the circuit board 8 are in contact with each other, and the chip 901 with the protective film includes the protective film 130'. Since the projecting electrode 91 during heating is more likely to melt than usual, the contact surface between the projecting electrode 91 and the connection pad 81 is wider than usual.
It should be noted that what is shown here is an example of a state in which the chip with the protective film and the circuit board are electrically connected, and the connection state is not limited to that shown here.

The chip placement step and the flip chip connection step in the manufacturing method can be performed by the same method as in the conventional manufacturing method of the substrate device, except that the chip with the protective film is used.
For example, heating of the chip with a protective film in the flip chip connection step can be performed using, for example, a reflow furnace equipped with a halogen heater. At this time, the chip with a protective film can be heated by, for example, irradiating near infrared rays in any or all wavelength ranges of 1400 to 1500 nm using a halogen heater.

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

<Raw material for manufacturing resin>
The official names of the resin manufacturing raw materials, which are abbreviated in this example and the reference example, are shown below.
BA: n-butyl acrylate MA: methyl acrylate HEA: 2-hydroxyethyl acrylate 2EHA: -2-ethylhexyl acrylate

<Raw material for manufacturing the composition for forming a protective film>
The raw materials used for producing the protective film forming composition 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 500,000, glass transition temperature -26 ° C) ..
[Thermosetting component (B1)]
(B1) -1: Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g / eq)
(B1) -2: Bisphenol A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800-900 g / eq)
(B1) -3: Dicyclopentadiene type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 255-260 g / eq)
[Thermosetting agent (B2)]
(B2) -1: Dicyandiamide ("ADEKA Hardener EH-3636AS" manufactured by ADEKA, thermally active latent epoxy resin curing agent, active hydrogen amount 21 g / eq)
[Curing accelerator (C)]
(C) -1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ" manufactured by Shikoku Chemicals Corporation)
[Filler (D)]
(D) -1: Silica filler (“SC2050MA” manufactured by Admatex Co., Ltd., silica filler surface-modified with an epoxy compound, average particle size 0.5 μm)
(D) -2: Spherical alumina (Showa Denko "CB-P02J", average particle size 3.0 μm)
(D) -3: Silica filler ("YA050C-MJA" manufactured by Admatex, average particle size 50 nm)
(D) -4: Stainless steel particles (particles obtained by crushing SUS304 to have an average particle size of 2.0 μm)
[Coupling agent (E)]
(E) -1: 3-Aminopropyltrimethoxysilane ("A-1110" manufactured by Nihon Unicar Co., Ltd.)
[Light Absorbent (I)]
(I) -1: 32 parts by mass of phthalocyanine blue dye (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow dye (Pigment Yellow 139), and 50 parts by mass of anthraquinone red dye (Pigment Red 177). A pigment obtained by mixing and pigmenting so that the total amount of the above three types of dyes / the amount of styrene acrylic resin = 1/3 (mass ratio).
(I) -2: Carbon black ("MA600" manufactured by Mitsubishi Chemical Corporation, average particle size 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: Diimonium dye ("CIR-1085F" manufactured by Carlit Japan, visible light and infrared absorber)

[Example 1]
<< Manufacture of protective film forming film >>
<Manufacturing of composition for forming protective film (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) are dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. By doing so, a thermosetting protective film forming composition (III-1) having a total concentration of all components other than the solvent of 45% by mass was obtained. The blending amounts of the components other than the solvent shown here are all the blending amounts of the target product containing no solvent.

<Manufacturing of protective film forming film>
A release film (second release film, "SP-PET50 1031" manufactured by Lintec Corporation, thickness 50 μm) in which one side of a polyethylene terephthalate film was peeled by a silicone treatment was used, and the peeled surface was obtained as described above. The protective film-forming composition (III-1) was applied and dried at 100 ° C. for 2 minutes to produce a thermosetting protective film-forming film having a thickness of 25 μm.

Further, the release film (first release film, "SP-PET38 1031" manufactured by Lintec Co., Ltd., thickness 38 μm) is peeled off on the exposed surface of the obtained protective film forming film on the side not provided with the second release film. By laminating the treated surfaces, the protective film forming film, the first release film provided on one surface of the protective film forming film, and the first release film provided on the other surface of the protective film forming film. A laminated film composed of two release films was obtained.

<< Evaluation of protective film >>
<Measurement of X _{max of protective film>}
The first release film was removed from the laminated film obtained above.
Next, the first release film was removed in an air atmosphere, and the protective film-forming film provided with the second release film was heat-treated at 145 ° C. for 2 hours to be thermoset to form a protective film.
Next, the second release film was removed from the protective film, and for the protective film, a UV-Vis spectrophotometer (“UV-VIS-NIR SPECTOPHOTOMETER UV-3600” manufactured by Shimadzu Corporation) was used, and an integrating sphere attached to the protective film was used. Instead, the absorbance was measured every 1 nm in the wavelength range of 1400 to 3200 nm including the near-infrared region. _{Then, X max} was obtained from the measurement result. The results are shown in Table 1.

<Measurement of S ₁₅₀ and S _{200 of protective film>}
The first release film was removed from the laminated film obtained above.
Next, the first release film was removed using an oven manufactured by ESPEC, and the protective film-forming film provided with the second release film was heat-cured at 145 ° C. for 2 hours to heat-cure the protective film. Formed.
Next, the second release film is removed from the protective film, and according to JIS K 7123: 2012, a differential scanning calorimeter (“PYRIS1” manufactured by PerkinElmer Co., Ltd.) is used, and the temperature rise rate is set to 10 ° C./min to 40. The differential scanning calorimetry of the protective film was measured under atmospheric pressure in the temperature range of ~ 250 ° C. 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 the protective film used. The results are shown in Table 1.

<Calculation of Z ₁₅₀ and Z _{200 of protective film>}
From the values of _{X max} , S ₁₅₀ and S ₂₀₀ obtained above _{, Z 150} and Z ₂₀₀ were calculated. The results are shown in Table 1.

<Measurement of T _{m of protective film>}
The first release film was removed from the laminated film obtained above.
Next, the first release film was removed in an air atmosphere, and the protective film-forming film provided with the second release film was heat-treated at 145 ° C. for 2 hours to be thermoset to form a protective film.
Next, the second release film was removed from the protective film, and the protective film was used with a UV-Vis spectrophotometer (“UV-VIS-NIR SPECTROPHOTOMETER UV-3600” manufactured by Shimadzu Corporation) and its attached integrating sphere was used. Instead, the light transmittance was measured every 1 nm in the wavelength range of 400 to 750 nm (that is, the visible light range). _{Then, T m} was obtained from the measurement result. The results are shown in Table 1.

<Measurement of _Um of protective film>
The first release film was removed from the laminated film obtained above.
Next, the first release film was removed in an air atmosphere, and the protective film-forming film provided with the second release film was heat-treated at 145 ° C. for 2 hours to be thermoset to form a protective film.
Next, the second release film was removed from the protective film, and the protective film was used with a UV-Vis spectrophotometer (“UV-VIS-NIR SPECTROPHOTOMETER UV-3600” manufactured by Shimadzu Corporation) to cover the near-infrared region from 1400 to 1400. In the wavelength range of 2600 nm, the amount of total light reflected light including the specular reflected light (normally reflected light) and the diffusely reflected light was measured every 1 nm by the SCI method. Further, for the barium sulfate reference plate, the amount of total light reflected light was measured by the same method. In either case, the sample folder is the "Large Sample Room MPC-3100" manufactured by Shimadzu Corporation, and the integrating sphere is the "Integrating Sphere Attached Device ISR-3100" manufactured by Shimadzu Corporation. The incident angle of the incident light was set to 8 °. Then, the ratio of the measured value on the protective film to the measured value on the reference plate ([measured value of the total light reflected light on the protective film] / [measurement of the total light reflected light on the reference plate]. Value] × 100), that is, the relative total light reflectance of the protective film was obtained, and this was adopted as the light reflectance. _{Then, U m} was obtained from the measurement result. The results are shown in Table 1.

<Measurement of maximum temperature reached of protective film during heating>
The first release film was removed from the laminated film obtained above, and the exposed surface of the protective film forming film formed by this was made of an 8-inch silicon wafer (thickness 350 μm) having no bumps (projected electrodes). It was affixed to the polished surface corresponding to the back surface. Further, the second release film was removed from the protective film forming film after the application to obtain a laminated body (1) formed by laminating the protective film forming film and the silicon wafer (first laminating step). ..

Next, the laminate (1) was heat-treated at 145 ° C. for 2 hours using an oven manufactured by ESPEC, thereby thermosetting the protective film-forming film to form a protective film (curing step).
Next, after slowly cooling the thermosetting laminate (1), a dicing tape is attached to the exposed surface of the protective film (that is, the surface opposite to the side on which the silicon wafer is provided). As a result, a laminated body (2') composed of a dicing tape (corresponding to a support sheet), a protective film, and a silicon wafer laminated in this order in the thickness direction was obtained (second laminating step).

Next, using a dicing blade, the silicon wafer in the laminate (2') is divided (diced) into a size of 20 mm × 20 mm, and the protective film is also cut to the same size to obtain a protective film after cutting. A silicon chip aggregate with a protective film was produced in which a large number of silicon chips provided on the back surface of the dicing tape were held in an aligned state on the dicing tape (division / cutting step).
Next, the silicon chip with a protective film in the silicon chip assembly with a protective film was separated from the dicing tape and picked up (chip acquisition step with a protective film).

The picked up silicon chip with protective film was placed on the conveyor. At this time, the silicon chip in the silicon chip with the protective film was brought into contact with the conveyor with the silicon chip facing downward, the protective film was turned upward, and the thermocouple was fixed while being in contact with the protective film. The silicon chip with a protective film in this state was conveyed to the inside of a reflow furnace (“WL-15-20DNX type” manufactured by Sagami Riko Co., Ltd.), and the silicon chip with a protective film was heated by using the halogen heater inside the furnace. At this time, the output adjustment knob (top surface NO.2 output VR) of the halogen heater was set to 100, which was equivalent to the heat treatment conditions provided in practice.
Then, using the thermocouple, the maximum temperature reached by the protective film during heating by the halogen heater was measured. The results are shown in Table 1.

<< Manufacturing of protective film forming film and evaluation of protective film >>
[Examples 2 to 21, Reference Examples 1 to 6]
The composition of the protective film-forming composition (III-1) at the time of production 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. A protective film-forming film was produced and the protective film was evaluated in the same manner as in Example 1 except that one or both of the types of components and the blending amount were changed. The results are shown in Tables 1-4.

As apparent from the above results, in Examples 1 to 21, the maximum temperature of the protective film during X _max measurements are at 254 ° C. or higher was significantly higher. This is because the protective film absorbs a large amount of light in the wavelength region including the near infrared region. When the temperature of the protective film-mounted chip mounted on the circuit board reaches such a region, the solder bumps on the chip melt and the electrical connection between the chip and the connection pad on the circuit board. It was confirmed in advance that the strength would be stronger. That is, the chip with a protective film provided with the protective film of Examples 1 to 21 on the back surface and having solder bumps on the circuit surface constitutes a substrate device having a strong connection strength with the circuit board and remarkably high reliability. I was able to confirm that it was possible.

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 light absorber (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 absorber (I) to the total content of all the components other than the solvent (that is, for forming a thermosetting protective film). The ratio of the content of the light absorber (I) to the total mass of the film for forming the heat-curable protective film in the film) was 2.2% by mass or more, and the ratio was high. Therefore, in Examples 1 to 21, it was presumed that the amount of light absorbed in the wavelength region including the near infrared region was large.

In Examples 1 to 21, the T _m was 2% or less, the transmittance of visible light was low, and the presence or absence of the protective film could be easily visually recognized.
In Examples 1 to 21, _{U m} is not more than 12%, the reflectance of near infrared rays was low. That is, in the protective film forming film of Examples 1 to 21, it was possible to form a protective film that easily raises the temperature during heating and a protective film that can suppress the malfunction of the device using near infrared rays. ..

On the other hand, in Reference Examples 1 to 6, _{the maximum temperature reached by the protective film at the time of Xmax} measurement was 248 ° C. or lower, which was lower than that of the above Examples. This is because it cannot be said that the protective film absorbs a large amount of light in the wavelength region including the near infrared region. When the temperature of the protective film-mounted chip mounted on the circuit board is in such a region, the solder bumps on the chip do not melt at all or are not sufficiently melted, and the chip and the connection pad on the circuit board It was confirmed in advance that no improvement in the electrical connection strength was observed. That is, a chip with a protective film having the protective film of Reference Examples 1 to 6 on the back surface and having solder bumps on the circuit surface does not improve the connection strength with the circuit board, and the reliability of the board device is improved. I was able to confirm that there was no such thing.

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 light absorbers (I) contained in the protective film forming film (composition (III-1)) were 2 to 4 types.
In Reference Examples 1 to 6, in the composition (III-1), the ratio of the content of the light absorber (I) to the total content of all the components other than the solvent (that is, for forming a thermosetting protective film). The ratio of the content of the light absorber (I) to the total mass of the film for forming the heat-curable protective film in the film) was 8.8% by mass or less, and the ratio was generally low.

<< Manufacturing of composite sheet for forming protective film >>
[Example 1]
Using the protective film-forming film obtained in Example 1 above, a protective film-forming composite sheet was subsequently produced. More specifically, it is as follows.
In the present specification, as the numbers of Examples and Reference Examples at the time of manufacturing the protective film forming composite sheet, Examples and References at the time of manufacturing the above-mentioned protective film forming film and at the time of evaluating the protective film are used. Continue to use the example numbers.

<Manufacturing of adhesive composition (I-4)>
It contains an acrylic resin (100 parts by mass) and a trifunctional xylylene diisocyanate cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (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) was prepared in which the total concentration of all the components of the above was 25% by mass. The contents of the components other than the methyl ethyl ketone shown here are all the contents of the target product containing no solvent.
The acrylic resin is an acrylic resin having a weight average molecular weight of 800,000 obtained by copolymerizing -2-ethylhexyl acrylate (80 parts by mass) and -2-hydroxyethyl acrylate (20 parts by mass). ..

<Manufacturing of support sheet>
A release film (“SP-PET38 1031” manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate film was peeled by a silicone treatment was used, and the pressure-sensitive adhesive composition obtained above was applied to the peeled surface. (I-4) was applied and dried by heating at 100 ° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm.

Next, as a base material, a polypropylene film (1) (thickness 80 μm, colorless) having one surface as a smooth surface and the other surface as an uneven surface was used, and the smooth surface obtained above was not used. A laminated sheet formed by laminating the exposed surfaces of the energy ray-curable pressure-sensitive adhesive layer, whereby the base material, the pressure-sensitive adhesive layer, and the release film are laminated in this order in these thickness directions, that is, peeling. A support sheet with a film was manufactured.

<Manufacturing of composite sheet for forming protective film>
The release film was removed from the support sheet obtained above. Further, the first release film was removed from the laminated film obtained in Example 1 (that is, the protective film forming film provided with the first release film and the second release film). Then, by adhering 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 base material and the adhesive are adhered. A protective film-forming composite sheet was produced in which the agent layer, the protective film-forming film, and the second release film were laminated in this order in this order of thickness.

[Examples 2 to 21, Reference Examples 1 to 6]
Protection is performed in the same manner as in Example 1 above, except that the laminated films obtained in Examples 2 to 21 and Reference Examples 1 to 6 are used instead of the laminated films obtained in Example 1. A composite sheet for film formation was manufactured.

<< Evaluation of protective film >>
<Measurement of X _max , S ₁₅₀ , S ₂₀₀ , T _m and U _m of protective film, and calculation _{of Z 150} and Z _{200 of protective film>}
The protective film X was used in the same manner as in Example 5 above, except that the composite sheet for forming the protective film obtained in Example 5 was used instead of the laminated film in Example 5. _max , S ₁₅₀ , S ₂₀₀ , T _m and U _m were measured, and Z _{150 and Z 200} of the protective film were calculated.
For example, _{when measuring Xmax} , the second release film is removed from the protective film-forming composite sheet, and the protective film-forming film in the protective film-forming composite sheet in this state is heat-treated at 145 ° C. for 2 hours. , Heat-cured to form a protective film. Then, the laminate of the base material and the pressure-sensitive adhesive layer (that is, the support sheet) was removed from the protective film, and the absorbance of this protective film was measured in the wavelength range of 1400 to 3200 nm. At the time of measuring S ₁₅₀ , S ₂₀₀ , T _m and U _m , the formation of a protective film and the measurement of these physical properties of the protective film were carried out in the same manner.

<Measurement of maximum temperature reached of protective film during heating>
The second release film was removed from the protective film-forming composite sheet obtained in Example 5 above, and the exposed surface of the protective film-forming film thus formed was 8 inches without bumps (projective electrodes). It was attached to a polished surface corresponding to the back surface of a silicon wafer (thickness 350 μm).

Next, the silicon wafer provided with the composite sheet for forming the protective film was heat-treated at 145 ° C. for 2 hours using an oven manufactured by ESPEC, thereby thermosetting the film for forming the protective film to form the protective film. (Curing step). As a result, a laminated body (3') in which the support sheet, the protective film, and the silicon wafer were laminated in this order in the thickness direction was obtained (lamination step).
After that, the silicon wafer is divided (diced), the protective film is cut (above, the division / cutting step), and protection is performed by the same method as in the case of the fifth embodiment except that the laminated body (3') is used. The silicon chip with a film was picked up (chip acquisition process with a protective film), and the maximum temperature reached by the protective film was measured.

As a result, are all the evaluation results of the protective film when the composite sheet for forming the protective film used here are exactly the same as the evaluation results in the previous Example 5 using the laminated film? Or, they are almost the same with negligible errors, and they are substantially the same.

INDUSTRIAL APPLICABILITY The present invention can be used for manufacturing various substrate devices including semiconductor devices.

101, 102, 103, 104 ... Composite sheet for forming a protective film, 10, 11 ... Support sheet, 10a, 20a ... One surface (first surface) of the support sheet, 11 ... Base material , 11a ... One surface (first surface) of the base material, 12 ... Adhesive layer, 13, 23 ... Protective film forming film, 130'... Protective film after cutting, 9.・ ・ Chip, 9b ・ ・ ・ Back side of chip

Claims (8)

A protective film forming film for forming a protective film on the back surface of the chip.
Using the maximum value _{X max} of the absorbance at a wavelength 1400~1500nm of the protective film, and a specific heat _{S 0.99} at 0.99 ° C. of the protective film, wherein:
Z ₁₅₀ = X _max / S _{150
Z 150} calculated by is 0.38 or more and
Wherein the _{X max,} the specific heat _{S 200} at 200 ° C. of the protective film, using the formula:
Z ₂₀₀ = X _max / S ₂₀₀
A film for forming a protective film, wherein _{Z 200} calculated by the above is 0.33 or more. The protective film forming film according to claim 1, wherein the protective film forming film is thermosetting or energy ray curable. The protective film forming film according to claim 1 or 2, wherein the protective film forming film contains two or more kinds of light absorbers capable of absorbing either one or both of visible light and infrared rays. The protective film forming film according to claim 1 or 2, wherein the protective film forming film contains a carbon material. Wherein the protective layer, the minimum value _{T m} of a transmittance of light having a wavelength of 400~750nm is 15% or less, for forming a protective film film according to any one of claims 1 to 4. Wherein the protective film, the maximum value _{U m} of the reflectance of light of wavelength 1400~1500nm is 20% or less, for forming a protective film film according to any one of claims 1 to 5. A support sheet and a protective film forming film provided on one surface of the support sheet are provided.
A 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 support sheet includes a base material and an adhesive layer provided on one surface of the base material.
The composite sheet for forming a protective film according to claim 7, wherein the pressure-sensitive adhesive layer is arranged between the base material and the film for forming a protective film.

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