TW202122527A - Film for forming protective film and composite sheet for forming protective film capable of improving electrical connection strength between a projecting electrode of a chip and a connecting pad on a circuit board - Google Patents

Abstract

A film for forming a protective film of the present invention is used to form a protective film on an inner surface of a chip. By using the maximum absorbance Xmax of the protective film at a wavelength of 1400 nm to 1500 nm, and the specific heat S150 of the protective film at 150 DEG C, Z150 calculated by the formula: Z150=Xmax/S150 is 0.38 or more, and by using the aforementioned Xmax and the specific heat S200 of the protective film at 200 DEG C, the Z200 calculated by the formula: Z200=Xmax/S200 is 0.33 or more. A composite sheet for forming a protective film of the present invention includes: a support sheet, and the film for forming the protective film which is provided on one surface of the support sheet.

Description

Film for forming protective film and composite sheet for forming protective film

The present invention relates to a film for forming a protective film and a composite sheet for forming a protective film. This application claims priority based on Japanese Patent Application No. 2019-184718 filed in Japan on October 7, 2019, and the content of the application is cited herein.

As a wafer such as a semiconductor wafer or an insulator wafer, there is a wafer in which a circuit is formed on one surface (circuit surface) of the wafer and further has protruding electrodes such as bumps on the surface (circuit surface). Such wafers are divided into chips, and the protruding electrodes are contacted with connection pads on the circuit substrate to be mounted on the circuit substrate. In such wafers or wafers, in order to suppress the occurrence of cracks and other damages, a protective film may be used to protect the surface (inner surface) opposite to the circuit surface (refer to Patent Literature 1 to Patent Literature 2).

In order to form such a protective film, a protective film forming film for forming a protective film is attached to the inner surface of the semiconductor wafer. In this case, it is possible to use a structure with a support sheet and a structure provided on one surface of the aforementioned support sheet. The composite sheet for protective film formation of the film for protective film formation mentioned above. The support sheet can be used as a dicing sheet for fixing the wafer when the inner surface of the wafer with the protective film forming film or the protective film is divided into chips. [Prior Technical Document] [Patent Document]

[Patent Document 1] JP 2015-32644 A. [Patent Document 2] International Publication No. 2015/146936.

[The problem to be solved by the invention]

As mentioned above, the chip-mounted circuit substrate is used as a substrate device for various electronic components. The electrical connection strength between the protruding electrode of the chip and the connection pad on the circuit substrate can be improved, and the manufacturing reliability can be higher.的substrate device. In response to this, Patent Literature 1 to Patent Literature 2 do not disclose a method for further improving such a connection strength.

The object of the present invention is to provide a protective film forming film for forming a protective film on the inner surface of a wafer, and a protective film forming composite sheet provided with the protective film forming film, which can improve the protruding electrodes and circuits of the wafer The electrical connection strength of the connection pads on the substrate. [Means to solve the problem]

The present invention provides a protective film forming film, which is used to form a protective film on the inner surface of a wafer; the maximum absorbance X _{max of the} protective film at a wavelength of 1400 nm to 1500 nm is used, and the specific heat S _{150 of the protective film at 150°C} , calculated by the _{Z 150 = X max / S 150} Z 150 is 0.38 or more and using the X _max, and the protective film in the specific heat of S _{200 200} ℃, by Z ₂₀₀ = X _max / S ₂₀₀ of the calculated Z ₂₀₀ is 0.33 or more. The film for forming a protective film of the present invention may be thermosetting or energy ray curable.

The film for forming a protective film of the present invention may contain two or more kinds of light absorbers that can absorb any one or two of visible light and infrared rays. The film for forming a protective film of the present invention may also contain a carbon material. _{In the film for forming a protective film of the present invention, the minimum value T m} of the transmittance of the protective film to light having a wavelength of 400 nm to 750 nm is preferably 15% or less. _{In the film for forming a protective film of the present invention, the maximum value U m} of the reflectance of the protective film for light having a wavelength of 1400 nm to 1500 nm is preferably 20% or less.

The present invention provides a composite sheet for forming a protective film, comprising: a support sheet; and a film for forming a protective film, which is provided on one surface of the support sheet; the film for forming a protective film is the film for forming a protective film of the present invention. In the composite sheet for forming a protective film of the present invention, the support sheet may include: a substrate; and an adhesive layer provided on one surface of the substrate; the adhesive layer may be disposed on the substrate and the protective film to form Use between membranes. [Efficacy of invention]

According to the present invention, there is provided a protective film forming film for forming a protective film on the inner surface of a wafer, and a protective film forming composite sheet provided with the aforementioned protective film forming film, which can improve the protruding electrodes of the wafer and the circuit board The electrical connection strength of the upper connection pad.

◇Protective film forming film The film for forming a protective film according to an embodiment of the present invention is used to form a protective film on the inner surface of a wafer, using the aforementioned protective film, the maximum absorbance X _max at a wavelength of 1400nm to 1500nm, and the aforementioned protective film to a specific heat S 150 deg.] C of _150, by the calculated sum _{Z 150 = X max / S 150} Z 150 is 0.38 or more; and using the X _max, and the protective film to a specific heat S 200 deg.] C of _200, with Z the calculated _{200 = X max / S 200 Z} 200 is 0.33 or more. The film for forming a protective film of this embodiment can be laminated with a support sheet as described below to form a composite sheet for forming a protective film.

The film for forming a protective film of this embodiment is used to provide a protective film on the inner surface of the chip to protect the film of the chip. The aforementioned protective film formation film is soft and can be attached to the wafer before being divided into chips.

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

In this specification, the so-called "energy line" refers to electromagnetic waves or charged particle beams with energy quantum. Examples of energy rays include ultraviolet rays, radiation rays, electron beams, and the like. The ultraviolet light can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In addition, in this specification, the "energy ray curability" means the property of being hardened by irradiation with energy rays, and the "non-energy ray hardening property" means the property of not being hardened even if the energy rays are irradiated. Furthermore, the so-called "non-curing" refers to the property that it does not harden even by any method such as heating or irradiation with energy rays. The non-curable protective film forming film is regarded as a protective film after it is installed (formed) on the target object.

In this specification, "wafers" include: semiconductor wafers made of elemental semiconductors such as silicon, germanium, selenium, or compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; and sapphire Insulator wafers composed of insulators such as, glass, etc. Circuits are formed on one surface of these wafers. In this specification, the surface of the wafer on which the circuits are formed is referred to as the "circuit surface". In addition, the surface of the wafer on the opposite side to the circuit surface is referred to as the "inner surface". Wafers are divided by dicing and other methods to become chips. In this specification, as in the case of a wafer, the surface of the chip on the side where the circuit is formed is called the "circuit surface", and the surface of the chip on the opposite side to the circuit surface is called the "inner 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 protruding electrode is preferably made of solder.

By using the protective film forming film of this embodiment or the protective film forming composite sheet provided with the protective film forming film, it is possible to manufacture a wafer with a protective film on the inner surface (sometimes referred to as "Chip with protective film").

Furthermore, by using the aforementioned wafer with a protective film, a substrate device can be manufactured. In this specification, the so-called "substrate device" means that a chip with a protective film is constructed by flip-chip connection to the connection pads on the circuit board with protruding electrodes on the circuit surface. For example, when a semiconductor wafer is used as the wafer, a semiconductor device can be cited as the substrate device. In the manufacturing process of the substrate device, a reflow furnace equipped with a halogen heater is sometimes used. By heating the circuit substrate on which the chip with the protective film is mounted, the protruding electrode on the chip with the protective film is melted to make The electrical connection between the protruding electrode and the connection pad on the circuit board becomes stronger.

The protective film obtained from the protective film forming film of this embodiment is that by setting Z _{150 to} be 0.38 or more and Z _{200 to} be 0.33 or more, the absorption of near-infrared rays during the aforementioned heating increases, and the temperature during heating It's higher than usual. Therefore, the protruding electrode on the wafer with the protective film also becomes a higher temperature due to the function of the protective film, which becomes a higher temperature, and the protruding electrode is easily melted under the influence of the high temperature. As a result, the protruding electrode and the circuit board The electrical connection strength of the upper connection pad becomes stronger than usual. By using a circuit board equipped with such a chip, a more reliable board device can be manufactured.

_{The Z 150} (=X _max ／S ₁₅₀ ) of the aforementioned protective film represents an index of the ease of temperature rise of the protective film at 150°C, and is 0.38 or more, for example, 0.41 or more, 0.45 or more, 0.55 or more, or 0.65 or more , 0.8 or more, 1.2 or more, 1.5 or more, 2 or more, and 2.5 or more. By setting Z ₁₅₀ to be greater than the aforementioned lower limit, the electrical connection strength between the aforementioned protruding electrode and the connection pad on the circuit board can be made stronger.

The _{upper limit of Z 150} is not particularly limited. For easier formation of a protective film meeting the above conditions of the Z _150, Z ₁₅₀ is preferably 4.2 or less.

Z ₁₅₀ can be adjusted appropriately within the range set by any combination of the above-mentioned lower limit and upper limit. For example, in one embodiment, Z _{150 is} preferably 0.38 to 4.2, and may be, for example, 0.41 to 4.2, 0.45 to 4.2, 0.55 to 4.2, 0.65 to 4.2, 0.8 to 4.2, 1.2 to 4.2, 1.5 to 4.2, 2 to 4.2, and any of 2.5 to 4.2. Among them, these numerical ranges are an example _{of Z 150.}

_{Z 200} (=X _max ／S ₂₀₀ ) of the aforementioned protective film represents an index of the ease of temperature rise of the protective film at 200°C, and is 0.33 or more, preferably 0.35 or more, and may be, for example, 0.4 or more and 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. By making Z ₂₀₀ greater than the aforementioned lower limit, the electrical connection strength between the aforementioned protruding electrode and the connection pad on the circuit board becomes stronger.

The _{upper limit of Z 200} is not particularly limited. For easier formation of Z meeting the above conditions of the protective film _200, Z ₂₀₀ is preferably 4 or less.

Z ₂₀₀ can be adjusted appropriately within the range set by any combination of the above-mentioned lower limit and upper limit. For example, in one embodiment, Z _{200 is} preferably 0.33 to 4, more preferably 0.35 to 4, and may be, for example, 0.4 to 4, 0.45 to 4, 0.52 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. Among them, these numerical ranges are one example _{of Z 200.}

The reason for specifying the protective film forming film of this embodiment using the specific heat of the protective film at 150°C and 200°C is because the circuit board on which the chip with the protective film is mounted is heated at a high temperature of 250°C or higher When heating is performed, the wafer with the protective film must be heated at a temperature of 150°C and 200°C.

_{The maximum value X max} of the absorbance of the aforementioned protective film at a wavelength of 1400 nm to 1500 nm is not particularly limited as long as it satisfies the above-mentioned _{conditions of Z 150} and Z _200. X _{max is} preferably 0.4 or more, more preferably 0.5 or more, and may be any of, for example, 0.6 or more, 0.9 or more, 1.2 or more, 1.6 or more, 2 or more, 2.4 or more, and 2.8 or more. X _{max is} preferably 4.5 or less, and may be any of 3.5 or less, 2.5 or less, 2 or less, 1.5 or less, 1.4 or less, 1.2 or less, and 0.99 or less, for example. The above-mentioned protective film system with X _max below the above-mentioned upper limit is easier to form. Furthermore, when near-infrared rays are irradiated, only the surface of the irradiated part and the vicinity of the surface will be rapidly heated. As a result, the irradiated part can be highly suppressed The surface is discolored or roughened.

X _max can be appropriately adjusted within a range set by any combination of any of the above-mentioned lower limit and any upper limit. For example, in one embodiment, X _{max is} preferably 0.4 to 4.5, more preferably 0.5 to 4.5, and may be, for example, 0.6 to 4.5, 0.9 to 4.5, 1.2 to 4.5, 1.6 to 4.5, 2 to 4.5, 2.4 to 4.5 , And any one of 2.8 to 4.5. In one embodiment, it is preferably 0.4 to 4.5, and may be, for example, 0.4 to 3.5, 0.4 to 2.5, 0.4 to 2, 0.4 to 1.5, 0.4 to 1.4, 0.4 to 1.2, And any one of 0.4 to 0.99. Among them, these numerical ranges are an example _{of X max.}

_{The specific heat S 150 of the} protective film at 150° C. is not particularly limited as long as it satisfies _{the conditions of the above-mentioned Z 150.} 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, particularly preferably 1.8 or less, particularly preferably 1.7 or less, and may also be 1.65 or less, for example.

S ₁₅₀ can be adjusted appropriately within the range set by any combination of any of the above-mentioned lower limit and any upper limit. For example, in one embodiment, S _{150 is} preferably 1 to 2, more preferably 1 to 1.9, particularly preferably 1 to 1.8, particularly preferably 1 to 1.7, and may also be, for example, 1 to 1.65. Among them, these numerical ranges are an example _{of S 150.}

_{The specific heat S 200 of the} protective film at 200° C. is not particularly limited as long as it satisfies _{the conditions of Z 200.} 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, particularly preferably 1.9 or less, particularly preferably 1.8 or less, and may also be, for example, 1.75 or less.

S ₂₀₀ can be adjusted appropriately within the range set by any combination of any of the above-mentioned lower limit and any upper limit. For example, in one embodiment, S _{200 is} preferably 1.1 to 2.1, more preferably 1.1 to 2, particularly preferably 1.1 to 1.9, particularly preferably 1.1 to 1.8, and may also be, for example, 1.1 to 1.75. Among them, these numerical ranges are an example _{of S 200.}

S ₁₅₀ and S ₂₀₀ are calculated based on JIS K 7123:2012, using a differential scanning calorimeter, and calculating the measured value of the differential scanning calorific value of the protective film obtained by setting the heating rate to 10°C/min.

_{The minimum value T m} of the transmittance of the aforementioned protective film for light with a wavelength of 400 nm to 750 nm is not particularly limited, and is preferably 15% or less, more preferably 10% or less, particularly preferably 7% or less, and particularly preferably 4% the following. By making T _m below the aforementioned upper limit value, the presence or absence of the protective film can be more easily recognized. The lower _{limit of T m} is not particularly limited. For example, T _m may be 0% or more.

_{The maximum value U m} of the reflectance of the aforementioned protective film for light with a wavelength of 1400 nm to 1500 nm is not particularly limited, and is preferably 20% or less, more preferably 15% or less, and particularly preferably 12% or less. By setting U _m to be equal to or less than the aforementioned upper limit value, the temperature of the protective film can be easily increased when the circuit board on which the chip with the protective film is mounted is heated. Furthermore, when using a wafer with a protective film, it is possible to suppress malfunctions of devices using near-infrared rays, such as near-infrared reflective sensors. The lower _{limit of U m} is not particularly limited. For example, U _m may be 0% or more. For easier formation of the protection film satisfying the above conditions of the U _m, U _m is preferably 0.2% or more, more preferably 0.5% or more, particularly preferably 1% or more. The reflectance of the protective film to light can be measured by the method described in the following examples.

In this embodiment, _{when the protective films of X max} , S ₁₅₀ and S ₂₀₀ are specified above, when the protective film forming film is thermosetting, it is preferable to heat the protective film forming film at 145°C for 2 hours the cured product is obtained in the case of forming the protective film is a film of the energy ray curable, preferably under the conditions of an illuminance cm 280mW / cm ^2, light quantity of 260mJ / ^2, the protective film is formed by irradiating the film 2 Hardened object obtained by energy rays. On the other hand, when the film for forming a protective film is non-curable, the protective films of X _max , S ₁₅₀ and S ₂₀₀ are formulated as the film for forming a protective film itself.

In this embodiment, when calculating the above-mentioned Z ₁₅₀ , X _max and S ₁₅₀ measured using the same protective film are used as X _max and S ₁₅₀ . Similarly, when calculating the above-mentioned Z ₂₀₀ , X _max and S ₂₀₀ measured using the same protective film are used as X _max and S ₂₀₀ .

In the case of thermally curing the protective film forming film to form a protective film, it is different from the case of curing by irradiating energy rays. Even if the thickness of the protective film forming film becomes thicker, it is sufficiently cured by heating. It can form a protective film with high protection performance. Furthermore, by a normal heating mechanism such as a heating oven, it is possible to heat and thermally harden a large number of protective film forming films together. When the protective film formation film is cured by irradiation of energy rays to form a protective film, unlike the case where it is thermally cured, the protective film formation composite sheet does not need to have heat resistance and can form a wide range of protective film formation Use composite tablets. Furthermore, it can be cured in a short time by irradiating energy rays. When the film for forming a protective film is used as a protective film without hardening, since the hardening step can be omitted, the subsequent steps can be simplified to manufacture a wafer with a protective film.

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

Regardless of whether the protective film forming film is curable or non-curable, and in the case of curable, regardless of whether it is thermosetting or energy ray curable, the protective film forming film can consist of one layer (single Layer), and may also be composed of a plurality of layers of two or more layers. When the film for forming a protective film is composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited. When the protective film formation film is composed of two or more layers, there is a possibility that the following problems may occur: the adhesion between the layers is poor, or the protection is based on the difference in the difficulty of expansion and contraction of each layer The film is warped and the protective film is peeled from the inner surface of the wafer. In terms of suppressing such defects, the protective film forming film is preferably composed of one layer.

In this specification, it is not limited to the case of the protective film forming film. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same or all the layers may be different, and only a part of the layers may be the same." The phrase "a plurality of 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".

Regardless of whether the protective film forming film is curable or non-curable, and in the case of curable, whether it is thermosetting or energy ray curable, the thickness of the protective film forming film is preferably 1 μm To 100 μm, more preferably 3 μm to 80 μm, particularly preferably 5 μm to 60 μm, and may be any of, for example, 10 μm to 50 μm, 15 μm to 40 μm, 17 μm to 38 μm, and 20 μm to 30 μm. By setting the thickness of the protective film forming film to be at least the aforementioned lower limit value, a protective film with higher protective ability can be formed, and furthermore, it is easier to form a protective film with high absorbance. By setting the thickness of the protective film forming film to be equal to or less than the aforementioned upper limit, it is possible to prevent the thickness from becoming too thick, and furthermore, the temperature of the protective film becomes easy to conduct to the wafer when the temperature rises. Here, the "thickness of the protective film formation film" means the overall thickness of the protective film formation film. For example, the thickness of the protective film formation film composed of a plurality of layers means the thickness of the protective film formation film The total thickness of all layers.

[Composition for Forming Protective Film] A film for forming a protective film can be formed using a composition for forming a protective film containing the constituent material of the film for forming a protective film. For example, the protective film formation film can be formed by coating the protective film formation composition on the surface to be formed of the protective film formation film, and drying it as needed. The ratio of the contents of the components that do not vaporize at room temperature in the protective film formation composition is usually the same as the ratio of the contents of the aforementioned components in the protective film formation film. In this specification, the "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C and the like.

The film for forming a thermosetting protective film can be formed using the composition for forming a thermosetting protective film, and the film for forming an energy ray curable protective film can be formed using the composition for forming an energy ray curable protective film, and it is non-curable protection. The film for film formation can be formed using the composition for non-curable protective film formation. In addition, in this specification, when the protective film forming film has two characteristics of thermosetting and energy ray curability, the contribution of the thermal curing of the protective film forming film to the formation of the protective film is greater than that of the energy ray curing. When making a contribution, the film for forming a protective film is regarded as a thermosetting film. On the contrary, when the contribution of the energy ray hardening of the protective film formation film to the formation of the protective film is greater than the contribution of the thermal hardening, the protective film formation film is regarded as the energy ray hardening film.

The composition for forming a protective film may be applied by a known method. For example, methods using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, roll Type coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, touch coater, etc.

Regardless of whether the protective film formation film is curable or non-curable, and when it is curable, whether it is thermosetting or energy-ray curable, the drying conditions of the protective film forming composition are not Specially limited. Among them, when the composition for forming a protective film contains the solvent described below, it is preferable to heat and dry it. In addition, the solvent-containing composition for forming a protective film is preferably heat-dried under the conditions of, for example, 70°C to 130°C and 10 seconds to 5 minutes. Among them, the composition for forming a thermosetting protective film is preferably heated and dried so that the composition itself and the film for forming a thermosetting protective film formed from the composition are not cured by heat.

Hereinafter, the film for forming a thermosetting protective film, the film for forming an energy ray curable protective film, and the film for forming a non-curing protective film will be described in order.

◎Film for forming a thermosetting protective film Regarding the curing conditions when the film for forming a thermosetting protective film is thermally cured to form a protective film, as long as the protective film has a degree of hardening sufficient to perform the function of the protective film, it is not particularly It is limited and may be appropriately selected depending on the type of film for forming a thermosetting protective film. For example, the heating temperature during thermal curing of the film for forming a thermosetting protective film is preferably 100°C to 200°C, more preferably 110°C to 170°C, particularly preferably 120°C to 150°C. In addition, the heating time during the thermal curing is preferably 0.5 hour to 5 hours, more preferably 0.5 hour to 4 hours, and particularly preferably 1 hour to 3 hours. The protective film formed by thermal curing is preferably gradually cooled to room temperature. The gradual cooling method is not particularly limited, and it may be static cooling.

By heating the film for forming a protective film at room temperature to a temperature higher than normal temperature, and then cooling to room temperature, it becomes a film for forming a protective film after heating and cooling. It is used for forming a protective film after heating and cooling at the same temperature. In the case of the hardness of the film and the hardness of the film for forming a protective film before heating, when the film for forming a protective film after heating and cooling is hard, the film for forming a protective film is thermosetting.

As a preferable film for thermosetting protective film formation, a film containing a polymer component (A), a thermosetting component (B), and a light absorber (I) is mentioned, for example. The polymer component (A) is regarded as a component formed by the polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component that undergoes a hardening (polymerization) reaction using heat as a trigger for the reaction. In addition, in this specification, a polymerization reaction also includes a polycondensation reaction.

[The composition for forming a thermosetting protective film (III-1)] A preferable composition for forming a thermosetting protective film includes, for example, the aforementioned polymer component (A), thermosetting component (B), and The thermosetting protective film forming composition (III-1) of the light absorber (I) (in this specification may be simply referred to as "composition (III-1)") and the like.

[Polymer component (A)] The polymer component (A) is used to impart film forming properties, flexibility, toughness, ductility, etc. to the film for forming a thermosetting protective film, and to impart flexibility and toughness to the protective film , Ductility and other ingredients. The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these polymer components The combination and ratio of (A) can be arbitrarily selected.

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

As the aforementioned acrylic resin in the polymer component (A), known acrylic polymers can be cited. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. By setting the weight average molecular weight of the acrylic resin to be equal to or higher than the aforementioned lower limit, the shape stability of the film for forming a thermosetting protective film (stability with time during storage) is improved. Furthermore, by making the weight average molecular weight of the acrylic resin below the aforementioned upper limit, the film for forming a thermosetting protective film becomes easy to follow the uneven surface of the adherend, and it is possible to further suppress the adhesion and thermal curing of the adherend. There are voids between the films for forming a protective film. In addition, in this specification, the "weight average molecular weight" is a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. By making the Tg of the acrylic resin more than the aforementioned lower limit, for example, the adhesive force between the cured product of the protective film forming film and the support sheet is suppressed, and the releasability of the support sheet is appropriately improved. Furthermore, by setting the Tg of the acrylic resin to the aforementioned upper limit or less, the adhesive force between the film for forming a thermosetting protective film and the cured product and the adherend of the film for forming a thermosetting protective film is improved.

When the acrylic resin has m types (m is an integer of 2 or more) of structural units, the m types of monomers derived from these structural units are assigned a non-repeated number from 1 to m and named as "monomers" In the case of m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox formula shown below.

(式中，Tg為丙烯酸樹脂的玻璃轉移溫度；m為2以上之整數；Tg_k 為單體m之均聚物的玻璃轉移溫度；W_k 為丙烯酸樹脂中的由單體m所衍生出之構成單元m的質量分率，其中，W_k 滿足下述式。)[Number 1]

(In the formula, Tg is the glass transition temperature of acrylic resin; m is an integer greater than 2; Tg _k is the glass transition temperature of the homopolymer of monomer m; W _k is the acrylic resin derived from monomer m The mass fraction of the constituent unit m, where W _k satisfies the following formula.)

(式中，m及W_k 與前述相同。)[Number 2]

(In the formula, m and W _{k are the} same as above.)

As the aforementioned Tg _k , a value described in a polymer material handbook, an adhesive handbook, or a polymer handbook can be used. For example, the methacrylate homopolymer Tg _k of 10 ℃, of a methyl methacrylate homopolymer Tg _k of 105 ℃, of 2-hydroxyethyl acrylate homopolymer Tg _k of -15 ℃.

Examples of acrylic resins include: 1 or 2 or more (meth)acrylate polymers; 1 or 2 or more (meth)acrylates and selected from (meth)acrylic acid and itaconic acid , Vinyl acetate, acrylonitrile, styrene and N-methylol acrylamide, etc., a copolymer of one or more monomers, etc.

Examples of the (meth)acrylate constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , N-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, (meth) )Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate Ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Alkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group is an alkyl (meth)acrylate with a chain structure of carbon number 1 to 18; (meth)acrylic acid rings such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate Alkyl esters; aralkyl (meth)acrylates such as benzyl (meth)acrylate; cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; di(meth)acrylate Cycloalkenyloxyalkyl (meth)acrylate such as cyclopentenoxyethyl; (meth)acrylimines; glycidyl-containing (meth) containing glycidyl (meth)acrylate, etc. Acrylate; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxyl-containing (meth)acrylates such as 2-hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; (meth)acrylic acid N-methylamino group (Meth)acrylates containing substituted amino groups such as ethyl esters, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

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

The acrylic resin may also have functional groups such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds. The aforementioned functional groups of the acrylic resin may be bonded to other compounds through the crosslinking agent (F) described below, or may be directly bonded to other compounds without the crosslinking agent (F). When the acrylic resin is bonded to other compounds via the aforementioned functional group, there is a tendency to improve the reliability of the package obtained by using the composite sheet for forming a protective film.

In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter sometimes simply referred to as "thermoplastic resin") may be used alone instead of the acrylic resin, or may be used in combination with the acrylic resin. By using the aforementioned thermoplastic resin, the peelability of the protective film self-supporting sheet may be improved, or the thermosetting protective film forming film may easily follow the uneven surface of the adherend, which can further suppress the heat on the adherend. There are voids and the like between the films for forming the curable protective film.

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

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

As said thermoplastic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

The aforementioned thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination and ratio of these thermoplastic resins You can choose any.

In the composition (III-1), regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components except the solvent (that is, the thermosetting protective film is formed) The ratio of the content of the polymer component (A) in the film to the total mass of the film for forming a thermosetting protective film) is preferably 5 mass% to 80 mass%, more preferably 8 mass% to 70 mass%, It is particularly preferably 11% by mass to 60% by mass, particularly preferably 14% by mass to 50% by mass, and may be any of, for example, 17% by mass to 45% by mass, and 20% by mass to 40% by mass. The protective film formation film and the protective film are generally thin, so when the protective film formation film or protective film with low toughness and fragility is used, when manufacturing a wafer with a protective film, the protective film formation film or the protective film The film has cracks (gaps). In this case, when heating the finally manufactured wafer with a protective film, there is a possibility that the heat transfer effect of the protective film from the high temperature to the protruding electrode on the wafer may decrease. However, by making the said ratio more than the said lower limit, the toughness of the film for protective film formation and a protective film becomes higher, and the effect of suppressing such a defect becomes high.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B) in this way, the composition (III-1) is regarded as containing the polymer Component (A) and thermosetting component (B).

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

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, polyimide resins, unsaturated polyester resins, and the like, and epoxy-based thermosetting resins are preferred.

[Epoxy-based 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 or two or more types. In the case of two or more types, these epoxy resins The combination and ratio of the thermosetting resin can be arbitrarily selected.

・Epoxy resin (B1) As the epoxy resin (B1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, Ortho-cresol novolak epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin Epoxy compounds with more than two functions.

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

As an epoxy resin having an unsaturated hydrocarbon group, for example, a compound obtained by substituting a part of the epoxy group of a polyfunctional epoxy resin with a group having an unsaturated hydrocarbon group is mentioned. Such a compound can be obtained, for example, by performing an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group. Furthermore, as an epoxy resin having an unsaturated hydrocarbon group, for example, a compound having a group having an unsaturated hydrocarbon group directly bonded to an aromatic ring constituting the epoxy resin or the like can be cited. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acrylic, The (meth)acrylamido group, etc., is preferably an acrylamido group.

The number-average molecular weight of the epoxy resin (B1) is not particularly limited, and the curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the protective film as the cured product of the film for forming the thermosetting protective film In terms of aspect, it is preferably 300 to 30,000, more preferably 300 to 10,000, and particularly preferably 300 to 3,000. The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 950 g/eq.

The epoxy resin (B1) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, the combination and ratio of these epoxy resins (B1) can be selected arbitrarily.

・Thermo-hardener (B2) The thermo-hardener (B2) functions as a hardener for epoxy resin (B1). As a thermosetting agent (B2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid group formed by anhydride, etc. are preferably The formed group is more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. Phenolic resin, etc. In the thermosetting agent (B2), examples of the amine curing agent having an amine group include dicyandiamide.

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

In the thermosetting agent (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin, etc. is preferably 300 to 30,000, More preferably, it is 400 to 10,000, particularly preferably 500 to 3,000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

A thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio of these thermosetting agents (B2) can be selected arbitrarily.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) relative to the content of the epoxy resin (B1) is 100 parts by mass, preferably 0.1 to 500 parts by mass , More preferably 0.1 parts by mass to 200 parts by mass, particularly preferably 0.1 parts by mass to 100 parts by mass, particularly preferably 0.5 parts by mass to 50 parts by mass, for example, 0.5 parts by mass to 25 parts by mass, 0.5 parts by mass to 10 parts by mass Parts by mass, and any one of 0.5 parts by mass to 5 parts by mass. By making the said content of a thermosetting agent (B2) more than the said lower limit, the film for thermosetting protective film formation becomes easy to harden. By making the aforementioned content of the thermosetting agent (B2) below the aforementioned upper limit, the moisture absorption rate of the thermosetting protective film formation film is reduced, and the reliability of the package obtained by using the protective film formation composite sheet is further improved Sex.

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)) relative to the polymer The content of component (A) is 100 parts by mass, preferably 10 parts by mass to 200 parts by mass, more preferably 20 parts by mass to 150 parts by mass, and may be, for example, 30 parts by mass to 100 parts by mass, 40 parts by mass to 80 parts by mass , And any one of 50 parts by mass to 70 parts by mass. By setting the aforementioned content of the thermosetting component (B) 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 releasability of the support sheet is improved.

[Light absorber (I)] The light absorber (I) is a component that absorbs light in a state where it is present in the protective film to easily increase the temperature of the protective film. When 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 it is easier to enlarge _{Z 150} and Z _200. Furthermore, since the transmittance of the protective film to light with a wavelength of 400 nm to 750 nm is reduced, the presence or absence of the protective film can be easily recognized.

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

Examples of the aforementioned organic pigments include diiminium-based pigments, ammonium-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, squalilium-based pigments, and azulene Pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalene lactam pigments, azo pigments, condensed azo pigments, Indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes , Thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indoxyphenol dyes, triallylmethane dyes, anthraquinone dyes, double Oxazine dyes, naphthol dyes, azomethine dyes, methine azo dyes, benzimidazolone dyes, pyranthrone dyes, threne dyes, and the like.

Examples of the aforementioned inorganic pigments include carbon materials such as carbon black, lanthanide-based materials, tin-based materials, antimony-based materials, and tungsten-based materials. The lanthanide-based materials, tin-based materials, antimony-based materials, and tungsten-based materials referred to herein refer to lanthanum-containing materials, tin-containing materials, antimony-containing materials, and tungsten-containing materials, respectively. Among these materials, the aforementioned inorganic pigment is preferably a carbon material, and more preferably carbon black in terms of superior dispersibility and less deterioration of the material itself due to heat.

The light absorber (I) is preferably capable of absorbing either or both of visible light and infrared light.

The light absorbing agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, these light absorbing agents The combination and ratio of (I) can be arbitrarily selected. For example, the composition (III-1) and the film for forming a thermosetting protective film may contain only one or two or more organic pigments, or only one or two or more inorganic pigments, or together One type or two or more types of organic pigments and inorganic pigments are used as the light absorber (I).

The composition (III-1) and the film for forming a thermosetting protective film preferably contain two or more kinds of light absorbers (I) that can absorb either or both of visible light and infrared rays, and more preferably contain two kinds of light absorbers (I) To 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 is preferable to contain a carbon material. In this case, for example, it may also contain carbon together. Materials and organic pigments.

In the composition (III-1), the ratio of the content of the light absorber (I) to the total content of all ingredients except the solvent (ie, the light absorber (I) in the film for forming a thermosetting protective film) The ratio of the content relative to the total mass of the film for forming a thermosetting protective film) is preferably 0.1% by mass to 20% by mass, more preferably 0.3% by mass to 17.5% by mass, and particularly preferably 0.5% by mass to 16% by mass , Particularly preferably 1% by mass to 15% by mass. By making the aforementioned ratio more than the aforementioned lower limit value, the effect of using the light absorber (I) can be more clearly obtained. By setting the aforementioned ratio to be equal to or less than the aforementioned upper limit, it is possible to suppress the use of excessive light absorber (I).

[Curing accelerator (C)] The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1). Examples of preferable hardening accelerators (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol. ; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (1 Phosphine in which more than one hydrogen atom is replaced by an organic group); tetraphenyl boron salt such as tetraphenyl phosphine tetraphenyl borate, triphenyl phosphine tetraphenyl borate, etc.

The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, these curing accelerators The combination and ratio of (C) can be arbitrarily selected.

In the case of using a curing accelerator (C), the content of the curing accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is relative to the content of the thermosetting component (B) 100 mass Parts, preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 7 parts by mass. By making the aforementioned content of the hardening accelerator (C) more than the aforementioned lower limit, the effect of using the hardening accelerator (C) can be more clearly obtained. By making the content of the hardening accelerator (C) below the aforementioned upper limit, for example, the hardening accelerator (C) with high polarity is prevented from becoming thermosetting in the film for forming a thermosetting protective film under high temperature and high humidity conditions. The adhesion interface side of the film for protective film formation and the adherend moves and the effect of segregation becomes high. As a result, the reliability of a wafer with a protective film obtained by using the composite sheet for forming a protective film is further improved.

[Filling material (D)] The composition (III-1) and the film for forming a thermosetting protective film may contain a filling material (D). When the thermosetting protective film forming film contains the filler (D), the thermosetting protective film forming film and the cured product (ie, protective film) of the thermosetting protective film forming film can easily adjust the thermal expansion coefficient , By optimizing the thermal 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. Furthermore, when the film for forming a thermosetting protective film contains the filler (D), the moisture absorption rate of the protective film can be reduced or the heat dissipation can be improved.

The filling material (D) can be any one of organic filling material and inorganic filling material, preferably inorganic filling material. As a preferable inorganic filler, for example, powders of silicon dioxide, stainless steel, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made into spheroids. Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica, alumina or stainless steel. When aluminum oxide is used, _{the adjustment of S 150} and S ₂₀₀ of the protective film becomes easier. Furthermore, when the protective film requires insulation, it is easy to impart insulation to the protective film. In the case of using stainless steel, _{the adjustment of S 150} and S ₂₀₀ of the protective film becomes particularly easy.

The average particle size of the filler (D) is not particularly limited, but is preferably 10 nm to 4000 nm, more preferably 30 nm to 3500 nm. By making the average particle size of the filler (D) within such a range, the effect of using the filler (D) can be more clearly obtained. For example, it is possible to easily increase the amount of the filler (D) in the composition (III-1) and the film for forming a thermosetting protective film, thereby facilitating the adjustment _{of S 150} and S _{200 of the protective film} In particular, the average particle size of the filler (D) is preferably 10 nm to 2500 nm, more preferably 20 nm to 1000 nm, particularly preferably 30 nm to 600 nm. On the other hand, in either case, the filler (D) whose average particle size is above the aforementioned lower limit has good operability, so the quality of the composition (III-1) is stable, and the use of a protective film is stably obtained In terms of the effect it brings, it is advantageous. _{In addition, the "average particle size" in this specification means the value of the particle size (D 50} ) at 50% of the cumulative value 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 film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these fillers (D) ) The combination and ratio can be selected arbitrarily.

In the case of using the filler (D), in the composition (III-1), the ratio of the content of the filler (D) to the total content of all ingredients except the solvent (ie, the film 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) is preferably 15% to 75% by mass, more preferably 18% to 70% by mass, and may be, for example Any of 45% to 70% by mass, 50% to 70% by mass, and 60% to 70% by mass. By setting the aforementioned ratio within such a range, the thermal expansion coefficient of the film for forming the thermosetting protective film and the cured product (ie, the protective film) of the film for forming the thermosetting protective film can be adjusted and the S of the protective film _{The adjustment of 150} and S ₂₀₀ has become 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 compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the film for forming a thermosetting protective film to the adherend can be improved. Furthermore, by using the coupling agent (E), the cured product of the film for forming a thermosetting protective film does not impair heat resistance and improves water resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (A) and the thermosetting component (B), and more preferably a silane coupling agent. As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxyoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc.

The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these coupling agents (E) ) The combination and ratio can be selected arbitrarily.

In the case of using the coupling agent (E), the content of the coupling agent (E) in the composition (III-1) and the thermosetting protective film formation film is relative to the polymer component (A) and the thermosetting component (B) The total content of) is 100 parts by mass, preferably 0.03 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, particularly preferably 0.1 parts by mass to 2 parts by mass. By making the aforementioned content of the coupling agent (E) above the aforementioned lower limit value, the following effect brought by the use of the coupling agent (E) can be obtained more obviously: improving the dispersibility of the filler (D) in the resin , Or improve the adhesion between the film for forming a thermosetting protective film and the adherend, etc. Furthermore, by making the aforementioned content of the coupling agent (E) below the aforementioned upper limit value, the generation of outgassing can be further suppressed.

[Crosslinking agent (F)] for the use of the above-mentioned acrylic resins having functional groups such as vinyl, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds as polymers In the case of the component (A), the composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The cross-linking agent (F) is a component used to bond the aforementioned functional groups in the polymer component (A) to other compounds for cross-linking. By cross-linking in this way, it is possible to adjust the thermosetting protective film formation. The initial adhesion and cohesion of the film.

Examples of the crosslinking agent (F) include organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking agents ( Crosslinking agent with aziridinyl group) and so on.

In the case of using an acrylic resin or the like having the aforementioned functional group as the polymer component (A), the composition (III-1) and the film for forming a thermosetting protective film may also contain a functional group that reacts with the aforementioned functional group by heating The crosslinking agent is used as the crosslinking agent (F). Examples of the crosslinking agent that reacts with the aforementioned functional group by heating include a blocked isocyanate compound in which an isocyanate group in an organic polyvalent isocyanate compound is blocked, a polyfunctional compound having transesterification reactivity, and the like.

The composition (III-1) and the crosslinking agent (F) contained in the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, these crosslinking agents The combination and ratio of (F) can be arbitrarily selected.

In the case of using the crosslinking agent (F), in the composition (III-1), the content of the crosslinking agent (F) relative to 100 parts by mass of the polymer component (A), preferably 0.01 to 20 parts by mass Parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, particularly preferably 0.5 parts by mass to 5 parts by mass. By making the aforementioned content of the cross-linking agent (F) more than the aforementioned lower limit, the effect of using the cross-linking agent (F) can be more clearly obtained. Furthermore, by making the aforementioned content of the crosslinking agent (F) below the aforementioned upper limit value, it is possible to suppress the use of an excessive amount of the crosslinking agent (F).

[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). The film for forming a thermosetting protective film contains energy-ray-curable resin (G) and can be irradiated with energy rays to change its characteristics.

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

As the aforementioned acrylate compound, for example, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ) Acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( (Meth)acrylates containing chain aliphatic skeletons such as meth)acrylates; (meth)acrylates containing cyclic aliphatic skeletons such as dicyclopentyl di(meth)acrylate; polyethylene di(meth)acrylates Polyalkylene glycol (meth)acrylate such as alcohol di(meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modification (Meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, etc.

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

The aforementioned energy ray curable compound used for polymerization may be only one type or two or more types. In the case of two or more types, the combination and ratio of these energy ray curable compounds 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, or two or more types. In the case of two or more types, these energy The combination and ratio of the linear curable resin (G) can be arbitrarily selected.

In the case of using energy ray curable resin (G), in the composition (III-1), the ratio of the content of the energy ray curable resin (G) to the total mass of the composition (III-1) is preferably 1 Mass% to 95% by mass, preferably 5% to 90% by mass, 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 energy ray curable resin (G), in order to make the energy ray curable resin (G) The polymerization reaction proceeds efficiently, and a photopolymerization initiator (H) may be contained.

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, and benzoin methyl benzoate. Benzoin compounds such as esters and benzoin dimethyl ketal; 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-methylpropanyl)benzyl)phenyl)-2-methylpropane-1- Acetophenone compounds such as ketones; bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. Phosphine oxide compounds; thioether compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisisobutyronitrile, etc. Azo compounds; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; Ketone; 2,4-Diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 1 -Quinone compounds such as chloroanthraquinone and 2-chloroanthraquinone. In addition, as the photopolymerization initiator (H), for example, photosensitizers such as amines can also be used.

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

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

[General-purpose additive (J)] The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range that does not impair the effect of the present invention. The general additives (J) may be well-known compounds, which can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred general additives include, for example, plasticizers, antistatic agents, antioxidants, and getters ( gettering agent), ultraviolet absorber, adhesion imparting agent, etc.

The general additives (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these general additives (J) ) The combination and ratio can be selected arbitrarily. The content of the general additive (J) of the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[Solvent] Composition (III-1) preferably further contains a solvent. The operability of the solvent-containing composition (III-1) becomes better. The aforementioned solvent is not particularly limited. Preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1- Alcohols such as butanol; 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 with amide bonds) Wait. The solvent contained in the composition (III-1) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these solvents can be arbitrarily selected.

Among the solvents contained in the composition (III-1), as a more preferable solvent, in terms of allowing the components contained in the composition (III-1) to be more uniformly mixed, for example, methyl ethyl Ketones, toluene, ethyl acetate, etc.

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

[Method for producing composition for forming thermosetting protective film] The composition for forming a thermosetting protective film, such as the composition (III-1), is obtained by blending the components constituting the composition. The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time. The method of mixing each component at the time of compounding is not particularly limited, as long as it is appropriately selected from the following known methods: a method of rotating a stirrer or a stirring blade, etc. for mixing; a method of mixing using a mixer; applying ultrasonic waves Methods of mixing, etc. Regarding the temperature and time when each component is added and mixed, as long as it does not deteriorate each compounding component, it is not particularly limited and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

◎The curing conditions when the energy ray curable protective film formation film is cured by energy ray curable protective film formation to form a protective film, as long as the protective film has a degree of curing that can fully perform the function of the protective film, There is no particular limitation, and it may be appropriately selected according to the type of the film for forming an energy ray curable protective film. For example, the illuminance of the energy ray when the energy ray of the film for forming an energy ray curable protective film is cured is preferably 60 mW/cm ² to 320 ^{mW/cm 2} . In addition, the amount of light of the energy ray during curing is preferably 100 mJ/cm ² to 1000 mJ/cm ² .

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

[Composition for forming energy ray curable protective film (IV-1)] As a preferable composition for forming energy ray curable protective film, for example, energy containing the aforementioned energy ray curable component (a) and a light absorber The composition (IV-1) for forming a linear curable protective film (in this specification may be simply referred to 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 irradiating energy rays. This component is also used to impart film-forming properties or properties to the film for forming an energy-ray curable protective film. Flexibility, etc., and form a hard protective film after curing. As the energy ray curable component (a), for example, a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000 can be cited (a2). The aforementioned polymer (a1) may be crosslinked at least partially by a crosslinking agent, or may not be crosslinked.

[Polymer (a1) having an energy-ray curable group and a weight average molecular weight of 80,000 to 2,000,000] As the polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, for example, acrylic resin ( a1-1) is formed by reacting an acrylic polymer (a11) with an energy ray curable compound (a12), and the acrylic polymer (a11) has a functional group capable of reacting with groups possessed by other compounds. The energy ray curable compound (a12) has a group that reacts with the aforementioned functional group and an energy ray curable group such as an energy ray curable double bond.

Examples of the aforementioned functional group that can react with groups possessed by other compounds include hydroxyl, carboxyl, amino, and substituted amino (one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. The base), epoxy and so on. Among them, in terms of preventing corrosion of circuits such as wafers or wafers, the aforementioned functional group is preferably a group other than a carboxyl group. Among these, the aforementioned functional group is preferably a hydroxyl group.

・Acrylic polymer (a11) having a functional group As the acrylic polymer (a11) having the aforementioned functional group, for example, an acrylic monomer having the aforementioned functional group and an acrylic monomer not having the aforementioned functional group are copolymerized. The resulting copolymer may also be a copolymer obtained by copolymerizing monomers other than acrylic monomers (non-acrylic monomers) in addition to these monomers. In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may also be adopted for the polymerization method.

Examples of acrylic monomers having the aforementioned functional groups include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amine group-containing monomers, epoxy group-containing monomers, and the like.

Examples of the aforementioned hydroxyl-containing monomers include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; vinyl alcohol , Allyl alcohol and other non-(meth)acrylic unsaturated alcohols (unsaturated alcohols without (meth)acrylic acid skeleton), etc.

Examples of the aforementioned carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid and itaconic acid , Maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. The (meth) carboxyalkyl acrylate and so on.

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

The acrylic monomer having the aforementioned functional group constituting the aforementioned acrylic polymer (a11) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these acrylic monomers can be arbitrarily selected.

Examples of acrylic monomers that do not have the aforementioned functional group include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth)acrylate Base) tridecyl acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Alkyl esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The group is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

Furthermore, as acrylic monomers that do not have the aforementioned functional groups, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate can also be cited. (Meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylate, etc.; aryl (meth)acrylates containing phenyl (meth)acrylate, etc. have aromatic Group-based (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N, Non-crosslinkable (meth)acrylates with tertiary amino groups such as N-dimethylaminopropyl ester.

The acrylic monomer that does not have the aforementioned functional group constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these acrylic monomers can be arbitrarily selected .

Examples of the aforementioned non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like. The aforementioned non-acrylic monomer constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these non-acrylic monomers can be arbitrarily selected.

In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the aforementioned functional group to the total amount of structural units constituting the acrylic polymer (a11) is preferably 0.1 Mass% to 50% by mass, more preferably 1% to 40% by mass, particularly preferably 3% to 30% by mass. By setting the aforementioned ratio to this range, the energy-ray curable properties of the acrylic resin (a1-1) obtained by the copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy-ray curable compound (a12) can be achieved The content of the base can adjust the degree of hardening of the protective film to a preferable range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these acrylic polymers (a11) may be Arbitrary choice.

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

・Energy ray curable compound (a12) The aforementioned energy ray curable compound (a12) preferably has one or two or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group. It is more preferable that the functional group of the polymer (a11) reacts with an isocyanate group as the aforementioned group. When the energy ray curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group and the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group easily react.

The number of the energy-ray-curable compound (a12) contained in one molecule is not particularly limited. For example, it can be appropriately selected in consideration of physical properties such as shrinkage rate required for the target protective film. For example, the aforementioned energy-ray-curable compound (a12) preferably has 1 to 5 of the aforementioned energy-ray-curable group in one molecule, and more preferably has 1 to 3.

Examples of the energy ray curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacrylic acid Isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl) ethyl isocyanate; by the reaction of diisocyanate compound or polyisocyanate compound and hydroxyethyl (meth)acrylate Acrylic monoisocyanate compound obtained; Acrylic monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate, etc. Among these, the aforementioned energy ray curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The aforementioned energy ray curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be only one type or two or more types. In the case of two or more types, these energy ray curable compounds (a12) The combination and ratio can be chosen arbitrarily.

In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferable It is 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, particularly preferably 50 mol% to 100 mol%. By setting the ratio of the aforementioned content in such a range, the adhesive force of the cured product of the film for forming an energy ray curable protective film becomes larger. In addition, in the case where the energy ray curable compound (a12) is a monofunctional (having one group in one molecule) compound, the upper limit of the ratio of the content becomes 100 mol%, but the energy ray curable compound (a12) When the sexual compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol%.

The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000. Here, the so-called "weight average molecular weight" is as described above.

The aforementioned polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be only one type or two or more types. In the case of two or more types, these polymers The combination and ratio of (a1) can be arbitrarily selected.

[Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000] As the aforementioned energy ray curable group in a compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000, examples include energy As the group of the linear hardenable double bond, preferred examples of the group include (meth)acryloyl group and vinyl group.

The aforementioned compound (a2) is not particularly limited as long as it satisfies the above-mentioned conditions. Examples thereof include low molecular weight compounds having energy ray curable groups, epoxy resins having energy ray curable groups, phenol resins having energy ray curable groups, etc. .

Among the aforementioned compounds (a2), examples of the low-molecular-weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and preferably acrylate compounds having a (meth)acryloyl group. As the aforementioned acrylate compound, for example, 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated Bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) Acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethyl Oxy) phenyl] 茀, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol 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, two Ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, new Pentylene glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis(meth)acryloyloxypropane and other bifunctional (methyl) ) Acrylate; Tris(2-(meth)acryloyloxyethyl) isocyanurate, ε-caprolactone modified isocyanurate tris-(2-(meth)acryloyloxyethyl) Base) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(methyl) ) Acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Meth)acrylate; (meth)acrylate urethane oligomer and other polyfunctional (meth)acrylate oligomers.

Among the aforementioned compounds (a2), as an epoxy resin having an energy ray curable group and a phenol resin having an energy ray curable group, for example, those described in paragraph 0043 of "JP 2013-194102 A" can be used. Resin. Such a resin is also equivalent to the resin constituting the thermosetting component described later, but it is regarded as the aforementioned compound (a2) in the composition (IV-1).

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

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

[Polymer without energy ray curable group (b)] The composition (IV-1) and the film for forming an energy ray curable protective film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a) In this case, it is preferable to further contain a polymer (b) that does not have an energy-ray curable group. The aforementioned polymer (b) may be crosslinked at least partially by a crosslinking agent, or may not be crosslinked.

Examples of the polymer (b) that does not have an energy-ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, acrylic urethane resins, etc. . Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter sometimes simply referred to as "acrylic polymer (b-1)").

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

Examples of the aforementioned acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and (meth) glycidyl groups. Acrylate, hydroxyl-containing (meth)acrylate, substituted amino group-containing (meth)acrylate, etc. The "substituted amino group" referred to herein is as described above.

As the aforementioned (meth)acrylic acid alkyl esters, for example, the acrylic monomers that do not have the aforementioned functional groups that constitute the acrylic polymer (a11) described above (the alkyl groups constituting the alkyl esters have a carbon number of 1 to The chain structure of 18 (meth)acrylic acid alkyl ester etc.) is the same compound.

Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (Meth)acrylic acid aralkyl ester such as benzyl acrylate; (meth)acrylic acid cycloalkenyl ester such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid dicyclopentenyloxy ethyl Cycloalkenyloxyalkyl (meth)acrylates such as esters and the like.

As said glycidyl group-containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example. Examples of the aforementioned hydroxyl-containing (meth)acrylate include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the aforementioned substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate and the like.

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 a polymer (b) which is cross-linked at least partly by a cross-linking agent and does not have the aforementioned energy ray curable group, for example, a reactive functional group in the aforementioned polymer (b) reacts with a cross-linking agent.的polymers. The aforementioned reactive functional group may be appropriately selected in accordance with the type of crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, as the aforementioned reactive functional group, a hydroxyl group, a carboxyl group, an amino group, etc. can be exemplified. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. Furthermore, when the crosslinking agent is an epoxy compound, the reactive functional group may include a carboxyl group, an amino group, an amide group, etc. Among these, a carboxyl group having high reactivity with an epoxy group is preferred. . Among them, in terms of preventing corrosion of the wafer or the circuit of the wafer, the reactive functional group is preferably a group other than a carboxyl group.

As a polymer (b) which has the said reactive functional group and does not have an energy-ray curable group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of acrylic polymer (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) are used with The monomer of the aforementioned reactive functional group may be sufficient. As the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth)acrylate may be mentioned. In addition, the above-mentioned polymer (b) may also be mentioned. A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms of the aforementioned acrylic monomer or non-acrylic monomer is substituted by the aforementioned reactive functional group.

In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of constituent units derived from a monomer having a reactive functional group to the total amount of constituent units constituting the polymer (b) It is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass. By setting the aforementioned ratio to this range, the degree of crosslinking in the aforementioned polymer (b) becomes a more preferable range.

In terms of the film forming properties of the composition (IV-1) becoming better, the weight average molecular weight (Mw) of the polymer (b) that does not have an energy ray curable group is preferably 10,000 to 2,000,000, more preferably Between 100,000 and 1,500,000. The "weight average molecular weight" referred to herein is as described above.

The composition (IV-1) and the polymer (b) that does not have an energy ray curable group contained in the film for forming an energy ray curable protective film may be only one type, or two or more types, or two types In the above case, the combination and ratio of these polymers (b) which do not have an energy-ray curable group can be arbitrarily selected.

As the composition (IV-1), a composition containing either or both of the aforementioned polymer (a1) and aforementioned compound (a2) can be cited. In addition, when the composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) that does not have an energy-ray curable group. In this case, it is also preferable to further Contains the aforementioned polymer (a1). Furthermore, the composition (IV-1) may not contain the aforementioned compound (a2), but may contain the aforementioned polymer (a1) and a polymer (b) that does not have an energy-ray curable group together.

In the case where the composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2), and the polymer (b) without an energy-ray curable group, in the composition (IV-1), the aforementioned compound ( The content of a2) is relative to 100 parts by mass of the total content of the aforementioned polymer (a1) and polymer (b) without energy ray curable groups, preferably 10 parts by mass to 400 parts by mass, more preferably 30 parts by mass To 350 parts by mass.

In the composition (IV-1), the ratio of the total content of the aforementioned energy ray curable component (a) and polymer (b) without energy ray curable group to the total content of components other than the solvent (ie The ratio of the total content of the aforementioned energy-ray-curable component (a) and the polymer (b) not having an energy-ray-curable group to the total mass of the aforementioned film in the film for forming an energy-ray curable protective film is preferably 5 mass% to 90 mass%, more preferably 10 mass% to 80 mass%, particularly preferably 20 mass% to 70 mass%. By setting the aforementioned ratio of the content of the energy ray curable component to this range, the energy ray curability of the film for forming an energy ray curable protective film becomes more favorable.

[Light Absorber] The aforementioned light absorber is a component that absorbs light in a state where it is present in the protective film to easily increase the temperature of the protective film. When the composition (IV-1) and the film for forming an energy ray curable protective film contain a light absorber, the X _{max of the} protective film becomes larger, and it is easier to enlarge _{Z 150} and Z _200.

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

The composition (IV-1) and the form of the film for forming an energy ray curable protective film containing the light absorber can be combined with the composition (III-1) and the form of the film for forming a thermosetting protective film containing the light absorber (I ) Is the same.

For example, the light absorber contained in the composition (IV-1) and the film for forming an energy ray curable protective film is preferably capable of absorbing either or both of visible light and infrared light.

The light absorbing agent contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be only one type or two or more types. In the case of two or more types, a combination of these light absorbing agents And the ratio can be chosen arbitrarily. For example, the composition (IV-1) and the film for forming an energy ray curable protective film may contain only one or two or more organic pigments, or only one or two or more inorganic pigments, or a combination of organic pigments. One or more of pigments and inorganic pigments are used as light absorbers.

The composition (IV-1) and the film for forming an energy ray curable protective film preferably contain two or more kinds of light absorbers that can absorb either or both of visible light and infrared rays, and more preferably contain two to seven kinds of light absorbers. Kind.

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 is preferable to contain a carbon material, and it is more preferable to contain a carbon material and an organic pigment together.

In the composition (IV-1), the ratio of the content of the light absorber to the total content of all ingredients except the solvent (that is, the content of the light absorber in the film for forming an energy ray curable protective film relative to the energy The ratio) of the total mass of the film for forming a linear curable protective film may be 0.1% by mass to 20% by mass. By making the aforementioned ratio more than the aforementioned lower limit value, the effect of using the light absorber can be more clearly obtained. By making the aforementioned ratio below the aforementioned upper limit value, it is possible to suppress the use of excessive light absorbers.

The composition (IV-1) and the film for forming an energy ray curable protective film may also correspond to the purpose, and may contain one that does not correspond to the energy ray curable component (a), the polymer (b), and the light absorber. Any one is one or two or more selected from the group consisting of thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, and general additives.

As the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, and general additives in the composition (IV-1), the thermosetting components in the composition (III-1) can be listed respectively. Compounds with the same components (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H) and general additives (J).

For example, when the composition (IV-1) contains a thermosetting component, by using such a composition (IV-1), the formed film for forming an energy ray curable protective film can be enhanced by heating The adhesive force to the adherend is also improved in the strength of the protective film formed by the film for forming the energy ray curable protective film.

In the composition (IV-1), the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, and general additives may be used singly, or two or more of them may be used in combination. In the case of more than one type, the combination and ratio of these can be arbitrarily selected.

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

In terms of improving the operability of the composition by dilution, the composition (IV-1) preferably further contains a solvent. Examples of the solvent contained in the composition (IV-1) include the same solvents as the solvent in the composition (III-1). The solvent contained in the composition (IV-1) may be only one type or two or more types. The content of the solvent of the composition (IV-1) is not particularly limited, and may be appropriately selected in accordance with the types of components other than the solvent, for example.

[Method for producing composition for forming energy ray curable protective film] The composition for forming an energy ray curable protective film, such as the composition (IV-1), is obtained by blending the components constituting the composition. The composition for forming an energy ray-curable protective film can be manufactured by the same method as the case of the composition for forming a thermosetting protective film described above, except for the difference in the types of ingredients.

◎ Film for forming a non-curable protective film As a preferable film for forming a non-curable protective film, for example, a film containing a thermoplastic resin, a light absorber, and a filler can be cited.

[Composition for forming a non-curable protective film (V-1)] A preferable composition for forming a non-curable protective film includes, for example, the formation of a non-curing protective film containing the aforementioned thermoplastic resin, light absorber, and filler Use the composition (V-1) (in this specification, it may only be referred to as the "composition (V-1)") and the like.

[Thermoplastic resin] The aforementioned thermoplastic resin is not particularly limited. As the aforementioned thermoplastic resins, more specifically, for example, acrylic resins, polyesters, polyurethanes, phenoxy resins, and polybutylene resins listed as components of the above-mentioned composition (III-1) can be cited. Non-curable resins such as olefin, polybutadiene, polystyrene, etc. are the same resins.

The aforementioned thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be only one type or two or more types. In the case of two or more types, the combination and ratio of these thermoplastic resins Can be chosen arbitrarily.

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

[Light Absorber] The aforementioned light absorber is a component that absorbs light in a state where it is present in the protective film to easily increase the temperature of the protective film. When the composition (V-1) and the non-curable protective film forming film contain a light absorber, the X _{max of the} protective film becomes larger, and it is easier to enlarge _{Z 150} and Z _200.

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

The composition (V-1) and the non-curable protective film forming film containing the light absorber can also be combined with the composition (III-1) and the thermosetting protective film forming film containing the light absorber (I ) Is the same.

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

The composition (V-1) and the non-curable protective film forming film may contain only one type of light absorber, or two or more types. In the case of two or more types, the combination of these light absorbers and The ratio can be selected arbitrarily. For example, the composition (V-1) and the film for forming a non-curable protective film may contain only one or two or more organic pigments, or only one or two or more inorganic pigments, or a combination of organic pigments. And one or two or more kinds of inorganic pigments as light absorbers.

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

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

In the composition (V-1), the ratio of the content of the light absorbing agent to the total content of all ingredients except the solvent (that is, the content of the light absorbing agent in the film for forming a non-curing protective film relative to the non-curing The ratio) of the total mass of the film for forming a protective film may be 0.1% by mass to 20% by mass. By making the aforementioned ratio more than the aforementioned lower limit value, the effect of using the light absorber can be more clearly obtained. By making the aforementioned ratio below the aforementioned upper limit, it is possible to suppress the use of excessive light absorbers.

[Filling material] The film system for forming a non-curable protective film containing a filler exerts the same effect as the film for forming a thermosetting protective film containing a filler (D).

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

The filler material contained in the composition (V-1) and the film for forming a non-curable protective film may be only one type or two or more types. In the case of two or more types, the combination and ratio of these filler materials may be Arbitrary choice.

In the composition (V-1), the ratio of the content of the filler to the total content of all ingredients except the solvent (that is, the content of the filler in the film for forming a non-curing protective film relative to the content of the non-curing protective film The ratio of the total mass of the film for film formation) is preferably 25% by mass to 75% by mass. By setting the aforementioned ratio to such a range, as in the case of using the composition (III-1), it becomes easier to adjust the thermal expansion coefficient of the film for forming a non-curable protective film (that is, the protective film).

The composition (V-1) may correspond to the purpose, and may contain other components that do not correspond to any of the thermoplastic resin, the light absorber, and the filler. The aforementioned other components are not particularly limited, and can be arbitrarily selected according to the purpose.

In the composition (V-1), the aforementioned other components may be used alone or in combination of two or more types. When two or more types are used in combination, the combination and ratio of these other components can be arbitrarily selected.

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

In terms of improving the operability of the composition by dilution, the composition (V-1) preferably further contains a solvent. Examples of the solvent contained in the composition (V-1) include the same solvents as the solvent in the above-mentioned composition (III-1). The solvent contained in the composition (V-1) may be only one type or two or more types. The content of the solvent in the composition (V-1) is not particularly limited. For example, it may be appropriately selected in accordance with the types of components other than the solvent.

[Method for producing composition for forming non-curable protective film] The composition for forming a non-curable protective film, such as the composition (V-1), is obtained by blending the components that constitute the composition. The composition for forming a non-curable protective film, for example, can be manufactured by the same method as the case of the composition for forming a thermosetting protective film described above, except for the difference in the types of ingredients.

Fig. 1 is a cross-sectional view schematically showing an example of a film for forming a protective film according to an embodiment of the present invention. In addition, the drawings used in the following descriptions are used to make it easier to understand the characteristics of the present invention. For convenience, the important parts may be enlarged and displayed, and the size ratio of each component is not limited to the case where it is the same as the actual situation. .

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

The film 13 for forming a protective film has the above-mentioned characteristics. The film 13 for protective film formation can be formed using the composition for protective film formation mentioned above.

Any one of the first release film 151 and the second release film 152 may be a well-known film. The first peeling film 151 and the second peeling film 152 may be the same films, or may be different films such as the peeling force required when peeling from the film-like adhesive 13 is different from each other.

The protective film formation film 13 shown in FIG. 1 removes any one of the first release film 151 and the second release film 152, and the resulting exposed surface becomes the one attached to the inner surface of the wafer (not shown) surface. In addition, the remaining one of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes a support sheet or a dicing sheet described later (also referred to as a "cutting tape" in this specification) The attached surface. For example, when the first surface 13a is the surface attached to the inner surface of the wafer, the second surface 13b is the attaching surface of the support sheet or the dicing sheet.

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

The protective film forming film of this embodiment can be attached to the inner surface of the wafer without being used in combination with the support sheet described later. In this 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 the 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 tool can be manufactured by cutting (ie, dividing the wafer) and cutting the protective film forming film or the protective film Protective film for wafers.

On the other hand, the film for forming a protective film of this embodiment can be used in combination with a support sheet described later to form a composite sheet for forming a protective film that can be formed and diced together. Hereinafter, such a composite sheet for forming a protective film will be described.

◇Composite sheet for forming a protective film The composite sheet for forming a protective film according to an embodiment of the present invention includes: a support sheet; and a film for forming a protective film provided on one surface of the support sheet, and the film for forming a protective film is the above-mentioned one. A film for forming a protective film according to an embodiment of the invention.

The composite sheet for forming a protective film of this embodiment is provided with the aforementioned film for forming a protective film, so that the electrical properties of the protruding electrodes in the wafer with the protective film and the connection pads on the circuit board can be made during the manufacturing process of the substrate device. The connection strength becomes stronger.

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

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

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

The support sheet may be transparent or opaque, and may be colored according to the purpose. For example, in the case where the film for forming a protective film has energy ray curability, the support sheet preferably allows the energy ray to penetrate.

As the support sheet, for example, a support sheet provided with a base material and an adhesive layer provided on one surface of the aforementioned base material; a support sheet composed only of the base material, and the like. When the support sheet is provided with an adhesive layer, the adhesive layer is arranged between the base material and the protective film formation film in the composite sheet for protective film formation.

In the case of using a support sheet provided with a base material and an adhesive layer, in the composite sheet for forming a protective film, the adhesive force or adhesion between the support sheet and the film for forming a protective film can be easily adjusted. In the case of using a support sheet composed only of a base material, a composite sheet for forming a protective film can be manufactured at low cost.

Hereinafter, with reference to the drawings, an example of the composite sheet for forming a protective film of the present embodiment will be described in accordance with the type of the support sheet.

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 addition, in the drawings following FIG. 2, elements that are the same as the elements shown in the already-explained drawings are given the same reference numerals as in the case of the already-explained drawings, and detailed explanations of the elements are omitted. The composite sheet 101 for forming a protective film shown here is configured to include: a support sheet 10; and a protective film formed on one surface of the support sheet 10 (sometimes referred to as the "first surface" in this specification) 10a膜13。 Film 13. The support sheet 10 is configured to include a base material 11 and an adhesive layer 12 provided on one surface (that is, the first surface) 11 a of the base material 11. In the composite sheet 101 for forming a protective film, the adhesive layer 12 is arrange|positioned between the base material 11 and the film 13 for forming a protective film. That is, the composite sheet 101 for forming a protective film is constructed by laminating the base material 11, the adhesive layer 12, and the film 13 for forming a protective film in this order in the thickness direction of these layers. The surface of the support sheet 10 on the side of the protective film formation film 13 (in this specification, sometimes referred to as the "first surface") 10a and the surface of the adhesive layer 12 opposite to the substrate 11 side (this specification , Sometimes referred to as "the first side") 12a is the same.

The composite sheet 101 for forming a protective film further includes an adhesive layer 16 for a jig and a release film 15 on the film 13 for forming a protective film. In the protective film forming composite sheet 101, the protective film forming film 13 is layered on the entire surface or substantially the entire area of the first surface 12a of the adhesive layer 12, and the protective film forming film 13 is on the side opposite to the adhesive layer 12 An adhesive layer 16 for jigs is laminated on a part of the surface 13a on the opposite side (in this specification, sometimes referred to as the "first surface") (that is, the area near the peripheral edge portion). Furthermore, the area where the adhesive layer 16 for jigs is not laminated on the first surface 13a of the film 13 for forming a protective film, and the adhesive layer 16 for jigs is on the opposite side to the side of the film 13 for forming a protective film The release film 15 is laminated on the surface (in this specification, sometimes referred to as the "first surface") 16a.

It is not limited to the case of the composite sheet for forming a protective film 101. In the composite sheet for forming a protective film of this embodiment, the release film (for example, the release film 15 shown in FIG. 3) has an arbitrary configuration. The composite sheet may or may not be provided with a release film.

In the composite sheet 101 for forming a protective film, a part of a gap may be formed between the release film 15 and the layer directly in contact with the release film 15. For example, although it is shown here that the side surface 16c of the adhesive layer 16 for jigs is in contact (laminated) with the release film 15, there may be cases where the side surface 16c does not contact the release film 15. In addition, although the first surface 13a of the protective film forming film 13 is in contact (laminated) with the release film 15 in the vicinity of the jig adhesive layer 16 here, there are also some areas that are not in contact. The case of peeling film 15. Furthermore, there are cases where the boundary between the first surface 16a and the side surface 16c of the adhesive layer 16 for jigs cannot be clearly distinguished. The above-mentioned point is the same also in the composite sheet for protective film formation of the other embodiment provided with the adhesive layer for jigs.

The adhesive layer 16 for jigs is a jig for fixing the composite sheet 101 for forming a protective film to a ring frame or the like. The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or may have a multiple-layer structure in which a double-area layer of a sheet used as a core material has an adhesive component-containing layer.

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

The composite sheet 101 for forming a protective film is used in the following manner: with the release film 15 removed, the inner surface of the wafer is attached to the first surface 13a of the film 13 for forming a protective film, and then the jig adhesive The first surface 16a of the layer 16 is attached to a jig such as a ring frame.

Fig. 3 is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film according to an embodiment of the present invention. The protective film forming composite sheet 102 shown here differs in the shape and size of the protective film forming film, and the jig adhesive is laminated on the first side of the adhesive layer instead of the first protective film forming film. Except for the surface, it is the same as the composite sheet 101 for forming a protective film shown in FIG. 1.

More specifically, in the composite sheet 102 for forming a protective film, the film 23 for forming a protective film is laminated on a partial area of the first surface 12a of the adhesive layer 12, that is, in the width direction of the adhesive layer 12 (Fig. 3 The area on the center side in the left-right direction). Furthermore, the adhesive layer 16 for jigs is laminated|stacked in the area|region where the film 23 for protective film formation is not laminated|stacked on the 1st surface 12a of the adhesive layer 12, ie, the area|region near the peripheral part. In addition, in the protective film forming film 23, the surface on the opposite side to the adhesive layer 12 side (in this specification, sometimes referred to as the "first surface") 23a and the first surface of the jig adhesive layer 16 A release film 15 is laminated on the surface 16a.

4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 103 for forming a protective film shown here is the same as the composite sheet 102 for forming a protective film shown in FIG. 3 except that it does not include the adhesive layer 16 for jigs.

Fig. 5 is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 104 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in FIG. 2 except that it is comprised with the support sheet 20 instead of the support sheet 10. The support sheet 20 is composed of only the base material 11. That is, the composite sheet 104 for protective film formation is comprised by laminating|stacking the base material 11 and the film 13 for protective film formation in the thickness direction of these layers. The surface of the support sheet 20 on the side of the protective film formation film 13 (in this specification, it may be referred to as the "first surface") 20a is the same as the first surface 11a of the base material 11. The base material 11 has adhesiveness at least on the first surface 11a.

The composite sheet for forming a protective film of this embodiment is not limited to the composite sheet for forming a protective film shown in Figs. A part of the structure of the composite sheet for film formation is changed or removed, or another structure is further added to the composite sheet for protective film formation described so far. More specifically, it is as follows.

So far, with regard to the composite sheet for forming a protective film having a support sheet composed of only a base material, only the composite sheet 104 for forming a protective film shown in FIG. The composite sheet for forming a protective film of the support sheet can also include, for example, the composite sheet 102 for forming a protective film shown in FIG. 3, or the composite sheet 103 for forming a protective film shown in FIG. 4, which does not have the protection of the adhesive layer 12 Composite sheet for film formation. However, this is only an example of another protective film forming composite sheet provided with a support sheet composed only of a base material.

So far, regarding the composite sheet for forming a protective film without an adhesive layer for jigs, only the composite sheet 103 for forming a protective film as shown in FIG. 4 is shown, but it is formed as a protective film without an adhesive layer for jigs Examples of the composite sheet include: the composite sheet 101 for forming a protective film shown in FIG. 2 without the adhesive layer 16 for jigs; the composite sheet for forming a protective film shown in FIG. 5 The sheet 104 does not include the composite sheet for forming a protective film of the adhesive layer 16 for jigs. However, this is only an example of another composite sheet for forming a protective film that does not have an adhesive layer for jigs.

So far, as the layers constituting the protective film forming composite sheet, although the base material, the adhesive layer, the protective film forming film, and the release film have been shown, the protective film forming composite sheet may be provided with layers that are not equivalent to these layers. Any other layer. The types of the aforementioned other layers are not particularly limited, and can be arbitrarily selected according to the purpose. The arrangement position, shape, size, etc. of the aforementioned other layers can also be arbitrarily selected according to the type of the layer, and is not particularly limited.

As the aforementioned other layer, for example, an intermediate layer that can impart any characteristics to the composite sheet for forming a protective film, etc., is arranged between the support sheet and the film for forming a protective film, and adjusts the film for forming the protective film or the protective film for forming The releasability of the cured product of the film from the supporting sheet, etc. However, this is only an example of the other protective film formation composite sheet provided with the other layer mentioned above.

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

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

○ Substrate The aforementioned substrate is in the form of a sheet or film, and various resins can be cited as a constituent material of the substrate. Examples of the aforementioned resin include polyethylene such as low density polyethylene (LDPE; Low Density Polyethylene), linear low density polyethylene (LLDPE: Linear Low Density Polyethylene), and high density polyethylene (HDPE; High Density Polyethylene); poly Polyolefins other than polyethylene such as propylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- (Meth) acrylate copolymers, ethylene-norbornene copolymers and other ethylene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resin obtained from ethylene as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Diesters, poly(ethylene-2,6-naphthalate), wholly aromatic polyesters with aromatic cyclic groups in all constituent units; copolymers of two or more of the aforementioned polyesters; poly(formaldehyde) Base) acrylate; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide Ether; polysulfide; polyether ketone and so on. In addition, examples of the resin include polymer alloys such as a mixture of the polyester and a resin other than the polyester. The polymer alloy of the aforementioned polyester and a resin other than the aforementioned polyester preferably has a relatively small amount of the resin other than the polyester. In addition, as the aforementioned resin, for example, a crosslinked resin obtained by crosslinking one or more of the aforementioned resins exemplified so far; using one or more of the aforementioned resins exemplified so far The modified resin such as ionic polymer.

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

The base material can be composed of one layer (single layer), or two or more layers. In the case of multiple layers, these multiple layers may be the same or different from each other. There is no special combination of these multiple layers. limited.

The thickness of the substrate is preferably 50 μm to 300 μm, more preferably 60 μm to 100 μm. By setting the thickness of the substrate in this range, the flexibility of the composite sheet for forming the protective film and the adhesion to the wafer are further improved. Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate.

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

The substrate may be transparent or opaque, may be colored according to the purpose, and may also be vapor-deposited with other layers. For example, when the film for forming a protective film has energy ray curability, it is preferable that the base material allows energy ray to penetrate.

In order to adjust the adhesion between the substrate and the layer provided on the substrate (such as an adhesive layer, a protective film forming film, or the aforementioned other layers), the surface of the substrate can also be treated with sandblasting, solvent treatment, etc. Concave-convex treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc. oxidation treatment; lipophilic treatment; hydrophilic treatment, etc. Furthermore, the surface of the substrate may also be primed.

The substrate may also have adhesiveness on at least one side by containing components (such as resin, etc.) in a specific range.

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

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

In this specification, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resin includes not only resins with adhesive properties, but also resins that exhibit adhesiveness by being used in combination with other ingredients such as additives, and exhibit adhesion by the presence of heat or water as a trigger. Sexual resin, etc.

The adhesive layer can be composed of one layer (single layer), or two or more layers. In the case of multiple layers, these multiple layers may be the same or different from each other. The combination of these multiple layers There is no particular limitation.

The thickness of the adhesive layer is not particularly limited, and is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, particularly preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.

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

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is coated on the surface to be formed of the adhesive layer, and dried as needed, so that the adhesive layer can be formed on the target site. The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the aforementioned components in the adhesive layer.

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

In the case of disposing the adhesive layer on the substrate, for example, the adhesive composition is coated on the substrate, and the adhesive composition is dried as needed, thereby laminating the adhesive layer on the substrate. Furthermore, when the adhesive layer is provided on the substrate, the adhesive layer can be laminated on the substrate by, for example, coating the adhesive composition on the release film, and drying it as needed, thereby An adhesive layer is formed in advance on the release film, and the exposed surface of the adhesive layer is attached to a surface of the substrate. The release film in this case may be removed at any point in the manufacturing process or use process of the composite sheet for forming a protective film.

Regardless of whether the adhesive layer is energy ray curable or non-energy ray curable, the drying conditions of the adhesive composition are not particularly limited. Among them, when the adhesive composition contains a solvent described later, it is preferable to heat and dry it. In addition, the adhesive composition containing the solvent is preferably heated and dried under the conditions of 70°C to 130°C for 10 seconds to 5 minutes, for example.

When the adhesive layer is energy ray curable, as the energy ray curable adhesive composition, for example, the following adhesive composition, etc.: The adhesive composition (I-1) contains non-energy ray hardening Adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)") and energy ray curable compound; adhesive composition (I-2), which is contained in non- Energy-ray curable adhesive resin (I-1a) with unsaturated groups introduced into the side chain of energy-ray curable adhesive resin (I-2a) (hereinafter, sometimes referred to as "adhesive resin (I-2a) )”); and the adhesive composition (I-3), which contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

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

[Adhesive resin (I-1a)] The aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3), and adhesive composition (I-4) (Hereinafter, these adhesive compositions are generally referred to as "adhesive composition (I-1) to adhesive composition (I-4)"). The aforementioned adhesive resin (I-1a) is preferably acrylic Resin.

As said acrylic resin, the acrylic polymer which has at least the structural unit derived from the alkyl (meth)acrylate, for example is mentioned. Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the aforementioned alkyl group is preferably linear or branched. shape.

The aforementioned acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. As the aforementioned functional group-containing monomer, for example, a monomer that can be a starting point for crosslinking by reacting the aforementioned functional group with the crosslinking agent described later; or can be a monomer that can be made by the aforementioned functional group and the aforementioned unsaturated group-containing monomer. The unsaturated group in the compound reacts to introduce the unsaturated group into the side chain of the acrylic polymer.

Examples of the aforementioned functional group-containing monomers include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, epoxy group-containing monomers, and the like.

In addition to the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the monomer containing a functional group, the said acrylic polymer may further have the structural unit derived from another monomer. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylates and the like. Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

In the adhesive composition (I-1) to the adhesive composition (I-4), the structural unit of the acrylic resin such as the acrylic polymer may be only one type or two or more types. In the case of two or more types, the combination and ratio of these structural units can be arbitrarily selected.

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

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

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

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

The aforementioned unsaturated group-containing compound not only has the aforementioned energy-ray polymerizable unsaturated group, but also has the ability to react with the functional group in the adhesive resin (I-1a) to react with the adhesive resin (I-1a) The compound of the bonded base. Examples of the energy ray polymerizable unsaturated group include (meth)acrylic acid group, vinyl (ethylene group), allyl group (2-propenyl group), etc., and (meth)acrylic acid group is preferred. base. Examples of groups that can be bonded to the functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amino groups, and carboxyl groups or epoxy groups that can be bonded The hydroxyl and amino groups, etc.

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

The adhesive composition (I-2) or the adhesive composition (I-3) may contain only one type of adhesive resin (I-2a), or two or more types, in the case of two or more types , The combination and ratio of these adhesive resins (I-2a) can be arbitrarily selected.

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

[Energy ray curable compound] As the energy ray curable compound in the adhesive composition (I-1) and the adhesive composition (I-3), there may be mentioned an energy ray polymerizable unsaturated group. A monomer or oligomer that is hardened by irradiation with energy rays.

Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. ) Poly(meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.; (meth)acrylic urethane Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of the oligomer include oligomers such as those exemplified by the polymerization of monomers above.

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

In the adhesive composition (I-1), the ratio of the content of the energy ray curable compound to the total mass of the adhesive composition (I-1) is preferably 1% to 95% by mass. In the adhesive composition (I-3), the content of the energy ray curable compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a).

[Crosslinking agent] In addition to having structural units derived from alkyl (meth)acrylates, the aforementioned acrylic polymers having structural units derived from functional group-containing monomers are used as adhesive resins (I-1a In the case of ), the adhesive composition (I-1) or the adhesive composition (I-4) preferably further contains a crosslinking agent. Furthermore, for example, when the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as the polymer in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), The adhesive composition (I-2) or the adhesive composition (I-3) may further contain a crosslinking agent.

The aforementioned crosslinking agent reacts with the aforementioned functional group, for example, to crosslink the adhesive resins (I-1a) or the adhesive resins (I-2a). Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy crosslinking agent such as ethylene glycol glycidyl ether (crosslinking agent with glycidyl group); aziridine such as hexa[1-(2-methyl)-aziridinyl] triphosphoryl triazine, etc. Pyridine crosslinking agent (crosslinking agent with aziridinyl group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate crosslinking agent (Crosslinking agent with isocyanuric acid skeleton) and so on.

The adhesive composition (I-1), the adhesive composition (I-2), or the adhesive composition (I-4) may contain only one type of crosslinking agent, or two or more types. In the case of two or more types, the combination and ratio of these crosslinking agents can be arbitrarily selected.

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

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

Examples of the aforementioned photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetophenone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, etc. Compounds; thioether compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile ; Titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzophenone; benzophenone; benzophenone; 2 ,4-Diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 1-chloroanthracene Quinone, 2-chloroanthraquinone and other quinone compounds. Furthermore, as the aforementioned photopolymerization initiator, for example, photosensitizers such as amines can also be used.

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

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

[Other additives] The adhesive composition (I-1) to the adhesive composition (I-4) may also contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, Known additives such as reaction delay agents and crosslinking accelerators (catalysts). In addition, the so-called reaction delay agent, for example, refers to the suppression of the effect of the catalyst mixed in the adhesive composition (I-1) to the adhesive composition (I-4), resulting in the adhesive composition ( I-1) To the components of the adhesive composition (I-4) that undergo cross-linking reactions outside the target. As the reaction delay agent, for example, a compound that forms a chelate complex by a chelate against a catalyst is exemplified. More specifically, a compound having two or more carbonyl groups (-C(= O)-) Compounds.

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

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

[Solvent] The adhesive composition (I-1) to the adhesive composition (I-4) may also contain a solvent. The adhesive composition (I-1) to the adhesive composition (I-4) contain a solvent to improve the applicability to the surface to be coated.

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

The solvent contained in the adhesive composition (I-1) to the adhesive composition (I-4) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these solvents Can be chosen arbitrarily.

The content of the solvent of the adhesive composition (I-1) to the adhesive composition (I-4) is not particularly limited, and may be adjusted appropriately.

○The manufacturing method of the adhesive composition The adhesive composition of the adhesive composition (I-1) to the adhesive composition (I-4) is prepared by mixing the aforementioned adhesive and components other than the aforementioned adhesive as required Obtained by the components used to make up the adhesive composition. For example, the adhesive composition can be manufactured by the same method as the case of the thermosetting protective film formation composition described above, except for the point that the types of the compounding components are different.

As another example of the preferred protective film forming film of the present embodiment, a protective film forming film is used to form a protective film on the inner surface of a wafer. The maximum absorbance of the protective film at a wavelength of 1400nm to 1500nm is used. value X _max, and the protective film to a specific heat S 150 deg.] C of _150, by the calculated sum _{Z 150 = X max / S 150} Z 150 is 0.38 or more; and using the X _max, and the protective film is the specific heat at 200 ℃ of S _200, calculated by the _{Z 200 = X max / S 200} Z 200 is 0.33 or more; the protective film containing the film-forming polymer component, the thermosetting component and the light absorbing agent; the polymer component is an acrylic resin; The thermosetting component is an epoxy-based thermosetting resin; the light absorber is one or two or more selected from the group consisting of organic pigments and inorganic pigments; the polymerization of the film for forming a protective film The ratio of the content of the material component to the total mass of the protective film forming film is 5 to 80% by mass; the content of the thermosetting component in the protective film forming film is relative to the content of the polymer component 100 The ratio of parts by mass is 10% by mass to 200 parts by mass; the ratio of the content of the light absorber in the film for forming a protective film to the total mass of the film for forming a protective film is from 0.1% by mass to 20% by mass.

◇Method for manufacturing composite sheet for protective film formation The aforementioned composite sheet for protective film formation can be manufactured by laminating the above-mentioned layers in a corresponding positional relationship, and adjusting the shape of a part or all of the layers as necessary. The formation method of each layer is as described above.

For example, in the case of laminating an adhesive layer on a substrate when manufacturing a support sheet, it is only necessary to apply the above-mentioned adhesive composition on the substrate and then dry it as needed. Furthermore, the adhesive layer can also be laminated on the substrate by the following method: apply an adhesive composition on the release film, and dry it as needed, thereby forming an adhesive layer on the release film in advance to make the adhesive The exposed surface of the agent layer is attached to one of the surfaces of the substrate. In this case, the adhesive composition is preferably applied to the release treatment surface of the release film. Although the case where the adhesive layer is laminated on the base material has been cited as an example so far, the above method can also be applied to, for example, the case where the intermediate layer or the aforementioned other layers are laminated on the base material.

On the other hand, for example, when a protective film forming film is laminated on an adhesive layer already laminated on a base material, the protective film forming composition can be coated on the adhesive layer to directly form the protective film forming film. For layers other than the protective film forming film, the composition for forming the layer can also be used, and the layer is laminated on the adhesive layer by the same method. In this way, a new layer (hereinafter referred to as the “second layer”) is formed on any layer that has been laminated on the substrate (hereinafter referred to as the “first layer”) to form a continuous two-layer laminate structure (in other words, the “second layer”). In the case of a layered structure of 1 layer and 2 layer), it can be applied to the method of coating the composition for forming the second layer on the first layer and drying it as needed. Among them, it is preferable to form a continuous two-layer laminated structure by using a composition for forming the second layer, and forming a second layer on the release film in advance, so that the second layer is relatively in contact with The side of the aforementioned release film is the exposed surface on the opposite side and is bonded to the exposed surface of the first layer. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. After the build-up structure is formed, the release film can be removed as needed. Here, the case where the protective film forming film is laminated on the adhesive layer is taken as an example, but for example, when an intermediate layer or the aforementioned other layers are laminated on the adhesive layer, the target laminated structure can be arbitrarily selected.

In this way, all layers other than the base material constituting the protective film forming composite sheet can be laminated by pre-formed on the release film and then bonded to the surface of the target layer. Therefore, as long as you need to appropriately select and adopt these steps It is sufficient to manufacture a composite sheet for forming a protective film.

In addition, the composite sheet for forming a protective film is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, a film for forming a protective film) on the opposite side to the support sheet in the composite sheet for forming a protective film. Thus, a composite sheet for forming a protective film with a release film is obtained by coating the release film (preferably the release treatment surface of the release film) with a composition for forming a protective film, etc. to form the most The composition of the surface layer is dried as needed to form a layer constituting the outermost layer on the release film in advance, and use any of the above on the exposed surface of the layer opposite to the side contacting the release film The method is to laminate the remaining layers without removing the release film and keep the attached state unchanged.

◇Method for manufacturing wafer with protective film (using method of protective film forming film and protective film forming composite sheet) The aforementioned protective film forming film and protective film forming composite sheet can be used for manufacturing the aforementioned protective film wafer.

[Manufacturing method 1] As a method of attaching the film for forming a protective film to a wafer without using a support sheet to manufacture a chip with a protective film, for example, the following manufacturing method of a chip with a protective film (in this specification Called "manufacturing method 1"), it has the following steps: the first build-up step is a process of attaching a protective film forming film to the inner surface of the wafer to obtain a wafer equipped with and set on the aforementioned wafer The layered body (1) of the film for forming the protective film on the inner surface, or the layered body (1') provided with the wafer and the protective film provided on the inner surface of the wafer; the second layering step is through The surface of the protective film forming film in the laminated body (1) is opposite to the wafer side, or the protective film in the laminated body (1') is opposite to the wafer The process of attaching the dicing sheet on the opposite side is the process of attaching the dicing sheet to obtain a laminate (2) by laminating the dicing sheet, the protective film forming film, and the wafer in sequence in the thickness direction of these layers. ), or a layered body (2') formed by sequentially layering the dicing sheet, the protective film, and the wafer in the thickness direction of these layers; the dividing/cutting step is performed by combining the layered body (2) The process of dividing the aforementioned wafer to produce a chip and cutting the aforementioned protective film forming film along the divided portion of the aforementioned wafer to obtain a cut-off piece provided with the aforementioned chip and the inner surface of the aforementioned chip A plurality of wafers with a film for forming a protective film formed of the film for forming a protective film are held on the dicing sheet to form a wafer assembly with a film for forming a protective film, or through the layered body (2') The process in which the wafer is divided to produce a chip and the protective film is cut along the divided portion of the wafer to obtain the chip provided with the chip and the cut protective film provided on the inner surface of the chip A plurality of wafers with protective films are held on the aforementioned dicing sheet to form a wafer assembly with protective film; and, the step of obtaining the wafers with protective film is performed by combining the aforementioned wafer assembly with a protective film forming film. A wafer with a protective film forming film, or a wafer with a protective film in the aforementioned chip assembly with a protective film is pulled from the dicing sheet and picked up to obtain a wafer with a protective film; in the aforementioned protective film When the forming film is curable, there is a curing step, which is from the step of attaching the protective film forming film to the inner surface of the wafer in the first layering step to the picking-up step of the wafer with the protective film In any stage after the wafer with the film for forming a protective film, the laminate (1), the laminate (2), the wafer assembly with the film for forming a protective film, or the wafer with the film for forming a protective film is used The protective film forming film in the wafer is cured to form a protective film, thereby producing the aforementioned laminated body (1'), laminated body (2'), a wafer assembly with a protective film, or a wafer with a protective film.

The film for forming a protective film used in the first build-up step of the manufacturing method 1 is the film for forming a protective film according to one embodiment of the present invention.

In the first layering step of manufacturing method 1, in the case where the protective film forming film is curable, the protective film forming film can be attached to the inner surface of the wafer, and then the attached protective film forming film can be made Hardening, thereby obtaining the aforementioned laminate (1'). On the other hand, when the film for forming a protective film is non-curable, the laminate (1') is directly obtained by sticking the film for forming a protective film on the inner surface of the wafer.

The aforementioned dicing sheet used in the second lamination step of the manufacturing method 1 may be a well-known dicing sheet.

The curing step may be performed at any stage as long as the protective film forming film is attached to the inner surface of the wafer in the first build-up step. For example, the hardening step can be carried out in any of the following stages: after the layered body (1) is obtained in the first layering step; between the first layering step and the second layering step; and the layered body is obtained in the second layering step ( 2) After; between the second layering step and the dividing/cutting step; after obtaining the wafer assembly with the protective film forming film in the dividing/cutting step; and the wafer with the protective film in the dividing/cutting step Between the obtaining steps; after picking up the wafer with the protective film forming film in the protective film obtaining step. In the case where the film for forming a protective film is non-curable, the manufacturing method 1 does not have the curing step.

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

The aforementioned first layering step, second layering step, dividing/cutting step, wafer obtaining step with protective film, and curing step in manufacturing method 1 are all except the use of the protective film forming film related to this embodiment. It can be performed by the same method as in the case of the conventional manufacturing method of a wafer with a protective film. For example, the thickness of the wafer to be attached to the protective film formation film is not particularly limited, but is preferably 20 μm to 600 μm, and more preferably 40 μm to 400 μm.

In the manufacturing method 1, the order of the division of the wafer in the division/cutting step and the cutting of the protective film formation film or the protective film may be exchanged. In this specification, the manufacturing method of such a wafer with a protective film is referred to as manufacturing method 2.

[Manufacturing method 2] That is, the manufacturing method 2 has: a cutting/dividing step of cutting the protective film forming film in the laminate (2) along the cutting portion of the protective film forming film The process of dividing the wafer to produce a wafer to obtain a plurality of wafers with protective film forming films, which are provided with the wafer and the cut protective film forming film provided on the inner surface of the wafer. A wafer assembly with a protective film forming film formed on the dicing sheet, or by cutting the protective film in the laminated body (2') and dividing the wafer along the cut portion of the protective film to produce The process of wafer manufacturing to obtain a wafer assembly with a protective film formed by a plurality of wafers with a protective film formed by the above-mentioned wafer and the above-mentioned protective film after cutting provided on the inner surface of the above-mentioned wafer and held on the dicing sheet body. The manufacturing method 2 is the same as the manufacturing method 1 except that it has a cutting/dividing step instead of the dividing/cutting step. That is, the manufacturing method 2 has the first layering step, the second layering step, the cutting/dividing step, and the wafer obtaining step with a protective film, and when the protective film forming film is curable, Any one from after the film for forming a protective film is attached to the inner surface of the wafer in the first layering step to after the wafer with the film for forming a protective film is picked up in the step of obtaining a wafer with a protective film There is a curing step in the stage, which hardens the protective film forming film in the aforementioned laminate (1), laminate (2), wafer assembly with a film for forming a protective film, or wafer with a film for forming a protective film. A protective film is formed, thereby producing the aforementioned laminated body (1'), laminated body (2'), a wafer assembly with a protective film, or a wafer with a protective film.

[Manufacturing method 3] A method of attaching a protective film forming composite sheet to a wafer as the aforementioned protective film forming film combined with a support sheet and manufacturing a protective film-equipped wafer, for example, includes the following protective film-equipped wafers The manufacturing method (referred to as "manufacturing method 3" in this specification) has: a lamination step, which is a process of attaching the protective film forming film in the protective film forming composite sheet to the inner surface of the wafer to obtain support A layered body (3) composed of a sheet, a protective film forming film, and a wafer sequentially stacked in the thickness direction of these layers, or a support sheet, a protective film, and a wafer are sequentially stacked in the thickness direction of these layers The laminated body (3') constituted by the upper build-up layer; the dividing/cutting step is to produce a wafer by dividing the wafer in the laminated body (3) and cut the protective film along the divided portion of the wafer The process of forming a film to obtain a plurality of wafers with protective film forming films comprising the wafer and the cut protective film forming film provided on the inner surface of the wafer. The wafers with protective film forming films are held on the support sheet. A chip assembly with a film for forming a protective film is formed, or a process in which a wafer is produced by dividing the wafer in the laminated body (3') and the protective film is cut along the divided portion of the wafer, To obtain a plurality of wafers with protective films formed by the above-mentioned wafers and the above-mentioned protective films after cutting provided on the inner surface of the above-mentioned wafers, which are held on the support sheet and have a wafer assembly with protective films; and The step of obtaining a protective film for the wafer is performed by removing the protective film-forming wafer from the protective film-forming wafer assembly or the protective film-forming wafer assembly from the protective film-forming wafer assembly. The support sheet is pulled apart and picked up to obtain a wafer with a protective film; in the case where the protective film forming film is curable, the protective film is further protected in the composite sheet for forming the protective film during the lamination step. After the film for film formation is attached to the inner surface of the wafer, there is a curing step in any of the steps from the picking up of the wafer with the film for protective film formation in the step of obtaining the wafer with the protective film. The body (3), a wafer assembly with a film for forming a protective film, or a film for forming a protective film in a wafer with a film for forming a protective film is cured to form a protective film, thereby producing the aforementioned laminated body (3'), A wafer assembly with a protective film, or a wafer with a protective film.

The film for forming a protective film used in the layering step of the manufacturing method 3 is the film for forming a protective film according to one embodiment of the present invention.

In the lamination step of manufacturing method 3, when the protective film forming film is curable, the protective film forming composite sheet can be attached to the inner surface of the wafer, and then the attached protective film forming composite sheet can be made The protective film forming film in the middle is cured, whereby the aforementioned laminate (3') can be obtained. On the other hand, when the film for forming a protective film is non-curable, the laminate (3') is directly obtained by attaching a composite sheet for forming a protective film on the inner surface of the wafer.

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

The curing step may be performed at any stage as long as the protective film forming film in the protective film forming composite sheet is attached to the inner surface of the wafer in the layering step. For example, the hardening step can be carried out in any of the following stages: after the layered body (3) is obtained in the layering step; between the layering step and the dividing/cutting step; in the dividing/cutting step, the protective film is formed After the wafer assembly of the film; between the dividing/cutting step and the step of obtaining a wafer with a protective film; after picking up the wafer with a film for forming a protective film in the step of obtaining a wafer with a protective film. In the case where the film for forming a protective film is non-curable, the manufacturing method 3 does not have the curing step.

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

In addition to the use of the composite sheet for forming a protective film related to this embodiment, the above-mentioned lamination step, dividing/cutting step, wafer obtaining step with protective film, and curing step in manufacturing method 3 can be used with the conventional protective film The same method as the case of the manufacturing method of the wafer is carried out. For example, the thickness of the wafer to be attached to the composite sheet for forming a protective film is not particularly limited, but is preferably 20 μm to 600 μm, and more preferably 40 μm to 400 μm.

[Other steps] The manufacturing method 1 may also be within the range that does not impair the effect of the present invention, except for the first lamination step, the second lamination step, the dividing/cutting step, the wafer obtaining step with a protective film, and the hardening step. In addition to the steps, there are other steps that are not equivalent to any of these steps. Similarly, the manufacturing method 2 may be within a range that does not impair the effects of the present invention, except for the first lamination step, the second lamination step, the cutting/dividing step, the wafer obtaining step with a protective film, and the hardening step. In addition, there are other steps that are not equivalent to any of these steps. Similarly, the manufacturing method 3 may be in a range that does not impair the effects of the present invention, except for the aforementioned lamination step, division/cutting step, wafer obtaining step with protective film, and hardening step, it does not correspond to these steps. Step of the other steps. In the case of any of manufacturing method 1 to manufacturing method 3, the types of the aforementioned other steps and the timing of performing the other steps may be arbitrarily selected according to the purpose, and are not particularly limited.

◇Method of manufacturing substrate device After obtaining a wafer with a protective film by the above-mentioned manufacturing method, except for using the wafer with a protective film, the substrate device can be manufactured by the same method as the conventional manufacturing method. As a manufacturing method of such a substrate device, for example, the following manufacturing method includes: a wafer arranging step in which protruding electrodes on a wafer with a protective film obtained by using the aforementioned protective film forming film are brought into contact with a circuit board The connection pad, whereby the chip with the protective film is arranged on the circuit substrate; and the flip-chip connection step is to use a halogen heater to heat the chip with the protective film arranged on the circuit substrate, thereby making The protruding electrode on the chip with the protective film is melted to improve the connection strength between the protruding electrode and the connection pad on the circuit board.

In the substrate device obtained by the aforementioned manufacturing method, by using the aforementioned chip with a protective film, the electrical connection strength between the protruding electrode and the connection pad on the circuit substrate becomes stronger than usual. Therefore, such a substrate device has high reliability. This is because in the aforementioned flip-chip connection step, as explained above, the protective film in the chip with protective film absorbs more near-infrared rays when heated, and the temperature of the protective film becomes higher than that of normal heating. For this reason. By the function of the protective film after becoming higher temperature, the protruding electrode on the chip with the protective film also becomes higher temperature, and the protruding electrode is easily melted under the influence of this, as a result, the protruding electrode and the connection pad on the circuit board The electrical connection strength becomes stronger than usual.

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

FIG. 6 is a cross-sectional view schematically showing the state after the chip with the protective film and the circuit substrate are electrically connected in the aforementioned flip-chip connection step. Here is shown the state after the chip 901 with the protective film and the circuit board 8 are electrically connected. The protective film-equipped wafer 901 is configured to include a wafer 9 and a cut protective film 130' provided on the inner surface 9b of the wafer 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. A protruding electrode 91 on the chip 9 and a connection pad 81 on the circuit board 8 are in contact with each other. By making the chip 901 with a protective film provided with a protective film 130', the protruding electrode 91 during heating is compared with the usual It is easier to melt, so the contact surface between the protruding electrode 91 and the connection pad 81 is wider than usual. In addition, what is shown here is an example of the state after the chip with the protective film and the circuit board are electrically connected, and the connection state is not limited to the state shown here.

The chip placement step and the flip chip connection step in the aforementioned manufacturing method can be performed by the same method as in the case of the conventional manufacturing method of the substrate device, except for the aspect of using the aforementioned chip with the protective film. For example, the heating of the chip with the 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, a halogen heater can be used to heat the wafer with the protective film by irradiating near infrared rays in any or all wavelength ranges from 1400 nm to 1500 nm, for example. [Example]

Hereinafter, the present invention will be described in detail through specific embodiments. However, the present invention is not limited to the examples shown below at all.

[Materials for the production of resins] The official names of the raw materials for the production of resins abbreviated in this embodiment and reference examples are shown below. BA: n-butyl acrylate MA: methyl acrylate HEA: 2-hydroxyethyl acrylate 2EHA: 2-ethylhexyl acrylate

[Production raw materials of the protective film forming composition] The raw materials used in the production of the protective film forming composition are shown below. [Polymer component (A)] (A)-1: Acrylic resin obtained by copolymerization of 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 epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184g/eq to 194g/eq) (B1)-2: Double Phenolic A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800g/eq to 900g/eq) (B1)-3: Dicyclopentadiene type epoxy resin ("Epiclon HP manufactured by DIC" -7200HH", epoxy equivalent 255g/eq to 260g/eq) [Thermal Hardener (B2)] (B2)-1: Dicyandiamide ("Adeka Hardener EH-3636AS" manufactured by ADEKA Corporation, thermally active latent ring Oxygen resin hardener, active hydrogen content 21g/eq) [hardening accelerator (C)](C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd. "Curezol 2PHZ") [filler (D)](D)-1: silica filler ("SC2050MA" manufactured by Admatechs, silica filler with epoxy compound surface modification, average particle size 0.5μm) ( D)-2: Spherical alumina ("CB-P02J" manufactured by Showa Denko Corporation, average particle size 3.0μm) (D)-3: Silica filler ("YA050C-MJA" manufactured by Admatechs Corporation, average particle size) Diameter 50nm) (D)-4: Stainless steel particles (SUS (Stainless Steel) 304 is crushed to make particles with an average particle diameter of 2.0 μm) [Coupling agent (E)] (E)-1: 3-amino group Propyl trimethoxysilane ("A-1110" manufactured by Nippon Unicar) [Light absorber (I)] (I)-1: 32 parts by mass of naphthalocyanine-based blue pigment (Pigment Blue 15: 3) , 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139) and 50 parts by mass of anthraquinone-based red pigment (Pigment Red 177) are blended to become the total amount of the aforementioned three pigments per styrene acrylic resin amount = 1/3 (mass ratio) of the pigment obtained by pigmentation. (I)-2: Carbon black ("MA600" manufactured by Mitsubishi Chemical Corporation, with an average particle size of 20nm) (I)-3: 2,3,9,10,16,17,23,24-octa(octyloxy) )-29H,31H-copper phthalocyanine (II) (manufactured by Sigma-Aldrich) (I)-4: 2,9,16,23-tetra-tert-butyl-29H,31H-copper phthalocyanine (II) (Sigma-Aldrich -Aldrich Co.) (I)-5: 2,11,20,29-Tetra-tert-butyl-2,3-naphthalocyanine (Sigma-Aldrich Co.) (I)-6: Diimonium dye ( "CIR-1085F" manufactured by Japan Carlit, visible light and infrared absorber)

[Example 1] [Production of protective film forming film] [Production of protective film forming composition (III-1)] The polymer component (A)-1 (150 parts by mass) and the 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), hardening 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) is dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain a thermosetting protective film with a total concentration of 45% by mass of all ingredients except the solvent Composition (III-1). In addition, the blending amounts of components other than the aforementioned solvents shown here are all blending amounts of the target substance without solvent.

[Manufacturing of protective film forming film] A peeling film made of polyethylene terephthalate film on one side was peeled off by a silicone treatment (the second peeling film, manufactured by Lindk Co., Ltd.) SP-PET50 1031", thickness 50μm), the above-obtained protective film forming composition (III-1) was coated on the release-treated surface of the release film, and dried at 100°C for 2 minutes to produce a thickness of 25μm A film for forming a thermosetting protective film.

Furthermore, a peeling film (the first peeling film, "SP-PET38 1031" manufactured by Lindek Co., Ltd., thickness 38μm) was attached to the exposed surface of the obtained protective film forming film on the side not equipped with the second release film. The peeling treatment surface obtains a structure including a protective film forming film, a first peeling film provided on one side of the protective film forming film, and a second peeling film provided on the other side of the protective film forming film Laminated film.

[Evaluation of protective film] [ _{Measurement of X max} of protective film] The first release film was removed from the laminated film obtained above. Then, in an air atmosphere, the protective film formation film provided with the second peeling film from which the first peeling film was removed was heat-treated at 145° C. for 2 hours to thermally cure the protective film to form a protective film. Next, the second release film was removed from the protective film. For the protective film, a UV-Vis spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation) was used for the protective film, and the spectrophotometer attached was not used. In the 1400nm to 3200nm wavelength region including the near infrared region, the absorbance is measured every 1nm. _{Then, X max is} 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. Then, by using an oven made by ESPEC, the protective film forming film with the second peeling film from which the first peeling film was removed was heat-treated at 145°C for 2 hours, and it was thermally cured to form a protective film. . Then, the second release film was removed from the aforementioned protective film, and then in accordance with JIS K 7123:2012, using a micro-difference scanning calorimeter ("PYRIS1" manufactured by PerkinElmer), the heating rate was set to 10°C/min. Measure the differential scanning heat of the protective film at a temperature range of 40°C to 250°C under atmospheric pressure. Then, calculate the heat flow at each temperature from the obtained heat flow diagram, and consider the usage of the protective film, and calculate the S ₁₅₀ and S _{200 of the} protective film. The results are shown in Table 1.

[Calculation of Z ₁₅₀ and Z ₂₀₀ of the _{protective film] Calculate Z 150} and Z ₂₀₀ from the values _{of X max} , S ₁₅₀ and S ₂₀₀ obtained above. 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. Then, in an air atmosphere, the protective film formation film provided with the second release film from which the first release film was removed was heat-treated at 145° C. for 2 hours to be thermally cured to form a protective film. Next, the second release film was removed from the protective film. For the protective film, a UV-Vis spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation) was used for the protective film, and the spectrophotometer attached was not used. Integrating sphere, and in the wavelength region of 400nm to 750nm (that is, the visible light region), the light transmittance is measured per 1nm. _{Then, T m is} obtained from the measurement result. The results are shown in Table 1.

[Measurement of U _m of Protective Film] The first release film was removed from the laminated film obtained above. Then, under an air atmosphere, the protective film formation film provided with the second release film from which the first release film was removed was heat-treated at 145° C. for 2 hours to heat-cured to form a protective film. Then, the second release film was removed from the aforementioned protective film, and for the protective film, a UV-Vis spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation) was used for the protective film at 1400nm including the near infrared region. In the wavelength range of 2600nm, the amount of total light reflection light including specular reflection light (regular reflection light) and diffuse reflection light is measured by SCI (Specular Component Included; including specular specular reflection light) per 1 nm. Furthermore, for a reference plate made of barium sulfate, the same method was used to measure the amount of light reflected by the total light. In either case, the "Large Sample Chamber MPC-3100" manufactured by Shimadzu Corporation is used as the sample holder, and the "Integrating Sphere Attachment ISR-3100" manufactured by Shimadzu Corporation is used as the integrating sphere. The incident angle of light is set to 8°. Then, calculate the ratio of the measured value in the protective film to the measured value in the reference plate ([Measurement value of the total light reflected light in the protective film]/[Light intensity of the total light reflected in the reference plate The measured value of]×100), that is, the relative total light reflectivity of the aforementioned protective film, and the reflectivity is used as the reflectivity of light. _{Then, U m is} obtained from the measurement result. The results are shown in Table 1.

[Measurement of the highest reaching temperature of the protective film during heating] The first release film was removed from the laminated film obtained above, and the exposed surface of the protective film forming film produced thereby was attached to the exposed surface of the protective film without bumps (protrusions). The inner surface (equivalent to the polished surface) of the 8-inch silicon wafer (thickness 350μm) of the shaped electrode. Furthermore, the second release film is removed from the film for forming a protective film after the attachment, and a laminate (1) in which the film for forming a protective film and a silicon wafer are laminated is obtained (first lamination step).

Then, the laminate (1) was heat-treated at 145°C for 2 hours using an oven manufactured by ESPEC Corporation, and the protective film formation film was thermally cured to form a protective film (curing step). Then, after the thermally hardened laminate (1) is gradually cooled, the exposed surface of the protective film in the laminate (1) (that is, the surface opposite to the side where the silicon wafer is provided) ) Attach a dicing tape to obtain a layered body (2') formed by sequentially layering the dicing tape (equivalent to a support sheet), a protective film, and a silicon wafer in the thickness direction of these layers (second layering step) ).

Then, using a dicing blade, the silicon wafer in the aforementioned laminate (2') is divided (cut) into a size of 20mm×20mm, and the protective film is also cut into the same size, thereby producing a The silicon wafer with the protective film after being cut is held as an assembly of silicon wafers with the protective film in a state in which they are arranged in plural on the dicing tape (dividing/cutting step). Then, the silicon wafer with a protective film in the assembly of silicon wafers with a protective film is pulled from the dicing tape and picked up (a step of obtaining a wafer with a protective film).

Place the picked up silicon wafer with protective film on the conveyor belt. At this time, the silicon wafer with the protective film faces downward to contact the conveyor belt, and the protective film faces upward so that the thermocouple is in contact with and fixed on the protective film. The silicon wafer with the protective film in this state is transferred to the inside of the reflow furnace (“WL-15-20DNX” manufactured by Sagami Riko Co., Ltd.), and the halogen heater located in the inside of the reflow furnace is used. The protective film of the silicon wafer is heated. At this time, set the output adjustment button of the halogen heater (No. 2 output VR above) to 100, which becomes the same as the practical heating treatment conditions. Then, using the aforementioned thermocouple, the highest reached temperature of the protective film at the time of heating by the halogen heater was measured. The results are shown in Table 1.

[Production of protective film forming film and evaluation of protective film] [Example 2 to Example 21, Reference Example 1 to Reference Example 6] Except for changing the formulation when manufacturing the protective film forming composition (III-1) Either or both of the type of the components and the amount of the ingredients so that the type and content of the components contained in the protective film forming composition (III-1) are as shown in Tables 1 to 4, they are all used in the examples In the same manner as in the case of 1, a protective film formation film was produced, and the protective film was evaluated. The results are shown in Table 1 to Table 4.

[Table 1] Example 1 2 3 4 5 6 7 Containing components (parts by mass) of the composition for forming a protective film Polymer component (A) (A)-1 150 150 150 150 150 150 150 Thermosetting component (B1) (B1)-1 60 60 60 60 60 60 60 (B1)-2 20 20 20 20 20 20 20 (B1)-3 20 20 20 20 20 20 20 Thermal hardener (B2) (B2)-1 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Hardening accelerator (C) (C)-1 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Filler (D) (D)-1 320 320 320 320 320 320 320 (D)-2 - - - - - - - (D)-3 - - - - - - - (D)-4 - - - - - - - Coupling agent (E) (E)-1 3 3 3 3 3 3 3 Light absorber (I) (I)-1 10 10 - - - - - (I)-2 2.7 - 1.2 2.2 2.7 3 4.7 (I)-3 - 5 - - - - - (I)-4 - 5 - - - - - (I)-5 - 10 - - - - - (I)-6 - 57 31 31 31 31 31 Light absorber (I) (species) contained in the protective film forming film 4 7 2 2 2 2 2 Evaluation result of protective film X _max 0.64 0.63 0.57 0.79 0.91 0.97 1.36 S ₁₅₀ 1.44 1.40 1.42 1.42 1.42 1.42 1.41 S ₂₀₀ 1.53 1.49 1.51 1.51 1.51 1.51 1.5 Z ₁₅₀ (=X _max / S ₁₅₀ ) 0.44 0.45 0.4 0.56 0.64 0.68 0.96 Z ₂₀₀ (=X _max / S ₂₀₀ ) 0.42 0.42 0.38 0.52 0.6 0.64 0.91 T _m (%) 0 2 0 0 0 0 0 U _m (%) 6 12 6 5 5 4 4 Maximum reach temperature during heating 260 257 255 268 268 274 278

[Table 2] Example 8 9 10 11 12 13 14 15 Containing components (parts by mass) of the composition for forming a protective film Polymer component (A) (A)-1 150 150 150 150 150 150 150 150 Thermosetting component (B1) (B1)-1 60 60 60 60 60 60 60 60 (B1)-2 20 20 20 20 20 20 20 20 (B1)-3 20 20 20 20 20 20 20 20 Thermal hardener (B2) (B2)-1 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Hardening accelerator (C) (C)-1 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Filler (D) (D)-1 120 120 80 400 400 400 400 400 (D)-2 - - - 50 50 50 100 100 (D)-3 - - - 50 50 50 140 140 (D)-4 - - - - - - - - Coupling agent (E) (E)-1 3 3 3 3 3 3 3 3 Light absorber (I) (I)-1 - - - - - - - - (I)-2 1.6 3 3.5 1.2 1.6 3.5 1.2 3 (I)-3 - - - - - - - - (I)-4 - - - - - - - - (I)-5 - - - - - - - - (I)-6 31 31 31 31 31 31 31 31 Light absorber (I) (species) contained in the protective film forming film 2 2 2 2 2 2 2 2 Evaluation result of protective film X _max 0.64 0.95 1.07 0.59 0.68 1.11 0.6 1.01 S ₁₅₀ 1.64 1.63 1.7 1.31 1.31 1.3 1.24 1.23 S ₂₀₀ 1.74 1.73 1.79 1.39 1.39 1.37 1.32 1.3 Z ₁₅₀ (=X _max / S ₁₅₀ ) 0.39 0.58 0.63 0.45 0.52 0.85 0.48 0.82 Z ₂₀₀ (=X _max / S ₂₀₀ ) 0.37 0.55 0.6 0.42 0.49 0.81 0.45 0.78 T _m (%) 0 0 0 0 0 0 1 0 U _m (%) 6 5 6 6 6 5 7 5 Maximum reach temperature during heating 254 263 262 262 268 280 263 273

[table 3] Example 16 17 18 19 20 twenty one Containing components (parts by mass) of the composition for forming a protective film Polymer component (A) (A)-1 150 150 150 150 150 150 Thermosetting component (B1) (B1)-1 60 60 60 60 60 60 (B1)-2 20 20 20 20 20 20 (B1)-3 20 20 20 20 20 20 Thermal hardener (B2) (B2)-1 2.2 2.2 2.2 2.2 2.2 2.2 Hardening accelerator (C) (C)-1 2.2 2.2 2.2 2.2 2.2 2.2 Filler (D) (D)-1 320 320 320 320 320 400 (D)-2 - - - - - - (D)-3 - - - - - 50 (D)-4 - - - - - 100 Coupling agent (E) (E)-1 3 3 3 3 3 3 Light absorber (I) (I)-1 10 10 10 10 10 10 (I)-2 - 8 11 14 18 twenty four (I)-3 - - - - - - (I)-4 - - - - - - (I)-5 - - - - - - (I)-6 66 - - - - - Light absorber (I) (species) contained in the protective film forming film 4 4 4 4 4 4 Evaluation result of protective film X _max 0.66 1.82 2.49 3.14 4 4.21 S ₁₅₀ 1.4 1.41 1.41 1.4 1.4 1.15 S ₂₀₀ 1.49 1.5 1.5 1.49 1.49 1.23 Z ₁₅₀ (=X _max / S ₁₅₀ ) 0.47 1.29 1.77 2.24 2.86 3.66 Z ₂₀₀ (=X _max / S ₂₀₀ ) 0.44 1.21 1.66 2.11 2.68 3.42 T _m (%) 2 0 0 0 0 0 U _m (%) 11 3 3 3 3 5 Maximum reach temperature during heating 258 280 275 281 282 288

[Table 4] Reference example 1 2 3 4 5 6 Containing components (parts by mass) of the composition for forming a protective film Polymer component (A) (A)-1 150 150 150 150 150 150 Thermosetting component (B1) (B1)-1 60 60 60 60 60 60 (B1)-2 20 20 20 20 20 20 (B1)-3 20 20 20 20 20 20 Thermal hardener (B2) (B2)-1 2.2 2.2 2.2 2.2 2.2 2.2 Hardening accelerator (C) (C)-1 2.2 2.2 2.2 2.2 2.2 2.2 Filler (D) (D)-1 320 320 120 80 320 320 (D)-2 - - - - - - (D)-3 - - - - - - (D)-4 - - - - - - Coupling agent (E) (E)-1 3 3 3 3 3 3 Light absorber (I) (I)-1 10 - - - 10 10 (I)-2 1.6 0.4 1.2 1.6 - - (I)-3 - - - - - - (I)-4 - - - - - - (I)-5 - - - - - - (I)-6 - 31 31 31 13 31 Light absorber (I) (species) contained in the protective film forming film 4 2 2 2 4 4 Evaluation result of protective film X _max 0.39 0.39 0.55 0.64 0.14 0.33 S ₁₅₀ 1.44 1.42 1.64 1.71 1.42 1.41 S ₂₀₀ 1.53 1.51 1.74 1.81 1.51 1.5 Z ₁₅₀ (=X _max / S ₁₅₀ ) 0.27 0.27 0.34 0.37 0.1 0.23 Z ₂₀₀ (=X _max / S ₂₀₀ ) 0.25 0.26 0.32 0.35 0.09 0.22 T _m (%) 0 1 0 0 12 6 U _m (%) 7 7 8 8 14 13 Maximum reach temperature during heating 239 239 244 248 235 241

From the above results, it can be seen that in Examples 1 to 21, _{the maximum reached temperature of the protective film at the time of X max} measurement was 254° C. or higher, which was significantly higher. This is because the protective film absorbs a large amount of light in the wavelength region including the near-infrared region. It has been confirmed in advance that when the temperature of a chip with a protective film mounted on a circuit board reaches such an area, the solder bumps on the chip will melt, and the electrical connection between the chip and the connection pad on the circuit board will be strengthened Become strong. That is, it was confirmed that the chip with the protective film of Example 1 to Example 21 on the inner surface and solder bumps on the circuit surface has strong connection strength with the circuit board, and the reliability of the structure is obvious. High substrate device.

In Examples 1 to 21, Z ₁₅₀ is 0.39 or more, and Z ₂₀₀ is 0.37 or more. In Example 1 to Example 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, the ratio of the content of the light absorber (I) in the composition (III-1) to the total content of all ingredients except the solvent (that is, for forming a thermosetting protective film) The ratio of the content of the light absorber (I) in the film to the total mass of the film for forming a thermosetting protective film) is 2.2% by mass or more, and the aforementioned ratio is high. Therefore, it is inferred that in Examples 1 to 21, the absorption amount of light in the wavelength region including the near-infrared region is large.

In Examples 1 to 21, the T _m is 2% or less, the visible light transmittance is low, and the presence or absence of the protective film can be easily recognized. Furthermore, in Examples 1 to 21, U _m is 12% or less, and the reflectance of near infrared rays is low. That is, the protective film forming films of Examples 1 to 21 can form a protective film whose temperature easily rises when heated, and a protective film that can suppress malfunctions of devices using near infrared rays.

In contrast, in Reference Example 1 to Reference Example 6, _{the maximum reach temperature of the protective film at the time of X max} measurement was 248° C. or less, which was lower than the case of the above-mentioned Examples. This is because it is difficult to say that the protective film absorbs light in a wavelength region including the near-infrared region. It has been confirmed in advance that the temperature of the chip with a protective film mounted on the circuit board is such an area that the solder bumps on the chip are not melted at all, or the melting is insufficient, and it cannot be regarded as the chip and the circuit board. The electrical connection strength of the connection pad has been improved. That is, it was confirmed that the connection strength of the chip with the protective film with the protective film of Reference Example 1 to Reference Example 6 on the inner surface and the solder bumps on the circuit surface and the circuit board was not improved, and it could not be considered as a substrate device The reliability has been improved.

In Reference Example 1 to Reference Example 6, Z ₁₅₀ is 0.37 or less, and Z ₂₀₀ is 0.35 or less. In Reference Example 1 to Reference Example 6, the light absorber (I) contained in the protective film forming film (composition (III-1)) was 2 to 4 types. In Reference Example 1 to Reference Example 6, the ratio of the content of the light absorber (I) in the composition (III-1) to the total content of all components except the solvent (that is, for forming a thermosetting protective film) The ratio of the content of the light absorber (I) in the film to the total mass of the film for forming a thermosetting protective film) is 8.8% by mass or less, which is generally low.

[Production of a composite sheet for forming a protective film] [Example 1] The film for forming a protective film obtained in Example 1 above was used, and then a composite sheet for forming a protective film was produced. More specifically, it is as follows. In addition, in this specification, the subsequent description is to maintain the numbers of the examples and reference examples at the time of the production of the protective film formation film and the evaluation of the protective film as the examples and the examples at the time of the production of the composite sheet for the protective film formation. Reference example number.

[Production of Adhesive Composition (I-4)] Preparation of non-energy-ray curable adhesive composition (I-4), containing acrylic resin (100 parts by mass), and trifunctional xylylene diisocyanate The coupling agent ("TAKENATE D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10 parts by mass) further contains methyl ethyl ketone as a solvent, and the total concentration of all components except the solvent is 25% by mass. In addition, the content of components other than methyl ethyl ketone shown here is the content of the target substance without solvent. The aforementioned acrylic resin is an acrylic resin obtained by copolymerizing 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (20 parts by mass), and has a weight average molecular weight of 800,000.

[Manufacturing of support sheet] Use a peeling film (SP-PET38 1031 manufactured by Lindeco, thickness 38μm) in which one side of a polyethylene terephthalate film is peeled off by silicone treatment ), apply the above-obtained adhesive composition (I-4) on the peeling treatment surface of the peeling film, and heat and dry at 100°C for 2 minutes to form a non-energy ray-curable adhesive layer with a thickness of 5μm .

Next, a polypropylene film (1) (thickness 80 μm, colorless) having a smooth surface on one side and an uneven surface on the other side was used as a substrate, and the non-energy ray obtained above was bonded to the smooth surface of the polypropylene film The exposed surface of the hardenable adhesive layer is used to produce a laminated sheet composed of a substrate, an adhesive layer and a release film in the thickness direction of these layers in sequence, that is, a support sheet with a release film.

[Production of a composite sheet for forming a protective film] The release film was removed from the support sheet obtained above. Furthermore, the first release film was removed from the laminated film obtained in Example 1 (that is, the protective film formation film provided with the first release film and the second release film). Then, the exposed surface of the adhesive layer produced by removing the above-mentioned release film and the exposed surface of the protective film forming film produced by removing the above-mentioned first release film are bonded together, thereby manufacturing a base material and an adhesive A composite sheet for forming a protective film composed of layers, a film for forming a protective film, and a second release film laminated in the thickness direction of these layers in this order.

[Example 2 to Example 21, Reference Example 1 to Reference Example 6] Using the laminated film obtained in Example 2 to Example 21 and Reference Example 1 to Reference Example 6 instead of the laminated film obtained in Example 1, Except for this, the same method as in the case of the above-mentioned Example 1 was used to manufacture a composite sheet for forming a protective film.

[Evaluation of protective film] [ _{Measurement of X max} , S ₁₅₀ , S ₂₀₀ , T _m and U _m of the protective film, and _{calculation of Z 150} and Z ₂₀₀ of the protective film] The protective film obtained in Example 5 above was used A composite sheet was used to replace the laminated film in Example 5 above. Except for this, the X _max , S ₁₅₀ , S ₂₀₀ , T _m and T m of the protective film were measured in the same manner as in Example 5 above. U _m , and calculate the Z ₁₅₀ and Z _{200 of the} protective film. For example, in _{the measurement of X max} , the second release film is removed from the composite sheet for forming a protective film, and the film for forming a protective film in the composite sheet for forming a protective film in this state is heated at 145°C for 2 hours , Make it thermally harden to form a protective film. Then, the laminate of the substrate and the adhesive layer (that is, the support sheet) was removed from the protective film, and the absorbance in the wavelength region of 1400 nm to 3200 nm was measured for the protective film. When measuring S ₁₅₀ , S ₂₀₀ , T _m and U _m , the formation of the protective film and the measurement of these physical properties of the protective film were also performed in the same manner.

[Measurement of the highest reaching temperature of the protective film during heating] The second release film was removed from the composite sheet for forming a protective film obtained in Example 5 above, and the exposed surface of the film for forming a protective film produced thereby was pasted Attached to the inner surface (equivalent to the polished surface) of an 8-inch silicon wafer (thickness 350μm) without bumps (protruding electrodes).

Then, using an oven manufactured by ESPEC Corporation, the silicon wafer provided with the protective film forming composite sheet was heat-treated at 145°C for 2 hours, thereby thermally curing the protective film forming film to form a protective film (curing step) . Thereby, a laminate (3') formed by laminating the support sheet, the protective film, and the silicon wafer in the thickness direction of these layers in order is obtained (layering step). From now on, except for the use of the laminate (3'), the same method as in the case of Example 5 above was used to divide the silicon wafer (dicing) and the protective film (the above is the division/ Cutting step), pick-up of silicon wafer with protective film (getting step of wafer with protective film), and measure the maximum reach temperature of the protective film.

As a result, the evaluation results of the protective film in the case of using the composite sheet for forming a protective film here are all the same or only negligible compared to the evaluation result of the above Example 5 using the laminated film. The errors are almost the same, but are substantially the same. [Industry Availability]

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

8: Circuit board 8a: The circuit surface of the circuit board 9: chip 9a: The circuit surface of the chip 9b: The inner surface of the chip 10, 20: support piece 10a, 20a: One side of the support sheet (the first side) 11: Substrate 11a: One side of the substrate (side 1) 12: Adhesive layer 12a: The first side of the adhesive layer 13,23: Film for forming protective film 13a, 23a: The first side of the protective film forming film 13b: The second side of the protective film forming film 15: Peel off the film 16: Adhesive layer for jigs 16a: The first side of the adhesive layer for jigs 16c: Side of the adhesive layer for jigs 81: connection pad 91: Protruding electrode 101, 102, 103, 104: Composite sheet for forming protective film 130’: Protective film after cutting 151: The first release film 152: The second release film 901: Chip with protective film

Fig. 1 is a cross-sectional view schematically showing an example of a film for forming a protective film according to an embodiment of the present invention. 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. Fig. 3 is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 5 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 6] Fig. 6 is a cross-sectional view schematically showing an example of the connection state of a wafer with a protective film and a circuit board when the film for forming a protective film according to an embodiment of the present invention is used.

10: Support piece

10a: One side of the support sheet (side 1)

11: Substrate

11a: The first side of substrate 11

12: Adhesive layer

12a: The first side of the adhesive layer 12

13: Film for forming protective film

13a: The first side of the protective film forming film

13b: The second side of the protective film forming film

15: Peel off the film

16: Adhesive layer for jigs

16a: The first side of the adhesive layer for jigs

16c: Side of the adhesive layer for jigs

101: Composite sheet for protective film formation

Claims (8)

A film for forming a protective film, which is used to form a protective film on the inner surface of a chip; using the maximum absorbance X _{max of the protective film at a wavelength of 1400 nm to 1500 nm and the specific heat S 150 of the} protective film at 150°C, by _{Z 150} calculated by the following formula is 0.38 or more: Z _{1 5 0} =X _max /S _{1 5 0} ; and using the aforementioned X _{max and the specific heat S 200 of the} aforementioned protective film at 200° C., the Z calculated by the following formula ₂₀₀ is 0.33 or more: Z _{20 0} =X _max /S _{20 0} . The film for forming a protective film according to claim 1, wherein the film for forming a protective film is thermosetting or energy ray curable. The film for forming a protective film according to claim 1 or 2, wherein the film for forming a protective film contains two or more kinds of light absorbers that can absorb one or both of visible light and infrared. The film for forming a protective film according to claim 1 or 2, wherein the film for forming a protective film contains a carbon material. The film for forming a protective film according to any one of claims 1 to 4, wherein the minimum value T _m of the transmittance of the protective film to light having a wavelength of 400 nm to 750 nm is 15% or less. The film for forming a protective film according to any one of claims 1 to 5, wherein the maximum value U _m of the reflectance of the protective film to light having a wavelength of 1400 nm to 1500 nm is 20% or less. A composite sheet for forming a protective film, comprising: a support sheet; and a film for forming a protective film, which is provided on one surface of the aforementioned support sheet; The film for forming a protective film is the film for forming a protective film as described in any one of claims 1 to 6. The composite sheet for forming a protective film according to claim 7, wherein the support sheet includes: a substrate; and an adhesive layer provided on one surface of the substrate; The said adhesive layer is arrange|positioned between the said base material and the said film for protective film formation.

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