TW202409235A - Protective film forming films, protective film forming composite sheets, kits, and uses of protective film forming films - Google Patents

Abstract

An object of the present invention is to provide an energy ray-curable protective film-forming film that has excellent near-infrared ray shielding properties and improves the protective film by setting the degree of curing of the protective film-forming film to an appropriate range during energy ray curing. The adhesiveness to the silicon wafer suppresses the peeling off of the protective film; and the use of a protective film forming composite sheet, a kit, and a protective film forming film having the protective film forming film. The present invention is a protective film-forming film that has energy ray hardening properties. The near-infrared ray transmittance of the protective film-forming film with a wavelength of 1300 nm is 10% or less. The measurement method of the protective film-forming film with a specific <hardening rate ratio >The measured hardening rate ratio ranges from 1.02 to less than 100.

Description

Protective film forming films, protective film forming composite sheets, kits, and uses of protective film forming films

The present invention relates to a protective film-forming film, a protective film-forming composite sheet, a kit, and uses of the protective film-forming film.

Some wafers, such as semiconductor wafers and insulator wafers, have circuits formed on one surface (circuit surface) and then have protruding electrodes such as bumps on this surface (circuit surface). Such a wafer is divided into chips, and the protruding electrodes are connected to the connection pads on the circuit board in a so-called face-down manner, thereby being mounted on the circuit board. In such a wafer or chip, in order to prevent damage such as cracks from occurring, a protective film may be used to protect the surface (inner surface) opposite to the circuit surface.

In order to form such a protective film, a protective film forming film for forming a protective film is attached to the inner surface of the wafer. The protective film forming film may be laminated on a support sheet for supporting the protective film forming film and used in the form of a composite sheet for protective film forming, or may be used without being laminated on a support sheet. After laser marking the protective film forming film, in order to improve the protective performance of the protective film forming layer, the semiconductor wafer is cut into chips by hardening by heat or energy beams as needed and picked up. Alternatively, after laser marking the protective film formed by hardening the protective film forming film by heat or energy beams, the semiconductor wafer is cut into chips and picked up. Next, the picked-up semiconductor chip with protective film is flip-chip connected to the connection pad on the circuit substrate of the motherboard, etc. The protruding electrodes on the chip with protective film are melted by heating the circuit substrate (hereinafter referred to as the reflow step), and the electrical connection between the protruding electrodes and the connection pad on the circuit substrate is consolidated, and then assembled on the circuit substrate.

Among the protective film-forming films, there are non-hardening protective film-forming films that do not have curability and function as a protective film in this state. When a non-hardening protective film is used to form a film, since a hardening step is not required, a wafer with a protective film can be manufactured at low cost by a simplified method. On the other hand, when a curable protective film-forming film is used, since a cured product of the protective film-forming film is used as a protective film, there is an advantage that the wafer protection capability is high. Then, a thermosetting protective film-forming film that is cured by heating requires a long time to be heated during curing, while an energy-ray-curable protective film-forming film that is cured by irradiating energy rays has a long time. It has the advantage that energy ray irradiation during hardening can be completed in a short time. Therefore, the development of various energy-beam curable protective film-forming films is progressing (see Patent Documents 1 to 3). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2010-031183. [Patent Document 2] International Publication No. 2017/188197. [Patent Document 3] International Publication No. 2019/082977.

[The problem that the invention wants to solve]

If a semiconductor device is exposed to near-infrared rays, there is a risk of malfunction. By using a protective film-forming film containing an inorganic pigment as a colorant, the light transmittance can be reduced, and the transmittance of near-infrared rays can be reduced. However, in the known energy-ray-curable protective film-forming film, only inorganic pigments are contained, and it is difficult to take into account both the purpose of reducing the transmittance of near-infrared rays and the purpose of energy-ray-curing the protective film-forming film to maintain the adhesion between the protective film and the silicon wafer when the protective film is formed. If the aforementioned adhesion is damaged, the protective film may become easy to peel off, and problems may occur in the subsequent manufacture of semiconductor devices.

The purpose of the present invention is to provide an energy-ray-curable protective film-forming film that has excellent near-infrared shielding properties, and by setting the degree of curing of the protective film-forming film to an appropriate range when the protective film-forming film is energy-ray-cured, it is possible to manufacture a semiconductor device with high reliability in which the adhesion between the protective film and the silicon wafer is improved and the peeling of the protective film is suppressed, as well as a protective film-forming composite sheet, a kit, and a use of the protective film-forming film having the protective film-forming film. [Means for solving the problem]

The present invention has the following aspects. [1] A protective film-forming film having energy ray curability; the protective film-forming film having a near-infrared transmittance of 1300 nm or less; and the protective film-forming film having a curing rate ratio of 1.02 or more and less than 100 as measured by the following curing rate ratio measurement method. ＜Curing rate ratio measurement method＞ The protective film-forming film is irradiated with ultraviolet rays from one side under the conditions of an illumination of 220 mW/ ^cm2 and a light quantity of 100 mJ/ ^cm2 to produce a protective film-forming film (100) after ultraviolet irradiation. Using a Fourier transform infrared spectrometer, the surface (inner surface) opposite to the surface irradiated with ultraviolet rays in the protective film forming film (100) before and after ultraviolet irradiation was subjected to FT-IR (Fourier-transform infrared) measurement at an incident angle of 45° and a diamond ATR (attenuated total reflectance) method. After the peak intensity of the peak near the wave number 790 cm ^-1 was normalized to 1.5 Abs and the deviation of the spectrum was corrected, the change in the peak intensity of the peak near the wave number 810 cm ^-1 in the inner surface of the protective film forming film (100) before and after ultraviolet irradiation was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film in 100 mJ/ ^cm2 . Next, a protective film forming film (500) after ultraviolet irradiation was prepared in the same manner as above except that ultraviolet irradiation was performed under the conditions of 220 mW/cm ² illumination and 500 mJ/cm ² light quantity. The surface (inner surface) opposite to the surface irradiated with ultraviolet ray in the protective film forming film (500) before and after ultraviolet irradiation was subjected to FT-IR measurement under the same conditions as above. After the peak intensity of the peak near the wave number 790 cm ^-1 was standardized to 1.5 Abs and the deviation of the spectrum was corrected, the change in the peak intensity of the peak near the wave number 810 cm ^-1 in the inner surface of the protective film forming film (500) before and after ultraviolet irradiation was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film in 500 mJ/cm ² . Next, the ratio of the curing rate of the inner surface of the protective film forming film at 500 mJ/ ^cm2 to the curing rate of the inner surface of the protective film forming film at 100 mJ/ ^cm2 is calculated by the following formula (2) and this is taken as the curing rate ratio of the protective film forming film. Curing rate = {(peak intensity before ultraviolet irradiation - peak intensity after ultraviolet irradiation) / peak intensity before ultraviolet irradiation} × 100 ・・・(1) Curing rate ratio = (curing rate of the inner surface of the protective film forming film at 500 mJ/ ^cm2 ) / (curing rate of the inner surface of the protective film forming film at 100 mJ/ ^cm2 ) ・・・(2) [2] The protective film forming film described in [1] contains an inorganic pigment as a coloring agent. [3] A composite sheet for forming a protective film, comprising: a support sheet, and a protective film forming film disposed on a surface of one side of the support sheet; the protective film forming film is the protective film forming film described in [1] or [2]. [4] A kit, comprising: a first laminate formed by sequentially laminating a first peeling film and a protective film forming film, and a support sheet for supporting a workpiece to which the protective film forming film is attached and the protective film forming film; the protective film forming film is the protective film forming film described in [1] or [2]. [5] A protective film forming film is used to form a protective film on the surface opposite to the circuit board in a semiconductor wafer or a semiconductor chip; the protective film forming film is the protective film forming film described in [1] or [2]. [Effect of the invention]

According to the present invention, it is possible to provide an energy ray-curable protective film-forming film that is excellent in near-infrared ray shielding properties and can be cured by setting the degree of curing of the protective film-forming film to an appropriate range during energy ray curing. To manufacture a highly reliable semiconductor device that improves the adhesion between a protective film and a silicon wafer and suppresses peeling of the protective film, and to provide a protective film forming composite sheet, a kit, and a protective film forming film having the protective film forming film. purpose.

◇Protective film forming film The protective film forming film of one embodiment of the present invention is an energy-ray-curable protective film forming film, the near-infrared transmittance of the protective film forming film at a wavelength of 1300nm is less than 10%, and the curing rate ratio of the protective film forming film measured by the following curing rate ratio measurement method is greater than 1.02 and less than 100.

<Method for measuring the curing rate ratio> The protective film forming film is irradiated with ultraviolet light from one side under the conditions of an illumination of 220 mW/ ^cm2 and a light quantity of 100 mJ/ ^cm2 to produce a protective film forming film (100) irradiated with ultraviolet light. The protective film forming film (100) before and after the ultraviolet light irradiation is subjected to FT-IR measurement at an incident angle of 45° and a diamond ATR method on the surface (inner surface) opposite to the surface irradiated with ultraviolet light of the protective film forming film (100) before and after the ultraviolet light irradiation. After the peak intensity of the peak near the wave number 790 cm ^-1 was normalized to 1.5 Abs and the deviation of the spectrum was corrected, the change in the peak intensity of the peak near the wave number 810 cm ^-1 on the inner surface of the protective film forming film (100) before and after the ultraviolet irradiation was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film in 100 mJ/cm ^2. Next, the protective film forming film (500) after ultraviolet irradiation was prepared in the same manner as above, except that the ultraviolet irradiation was performed under the conditions of 220 mW/cm ^{2 of illumination and 500 mJ/cm 2 of} light. The surface (inner surface) opposite to the surface irradiated with ultraviolet light in the protective film forming film (500) before and after the ultraviolet irradiation was subjected to FT-IR measurement under the same conditions as above. After the peak intensity of the peak near the wave number 790 cm ^-1 was normalized to 1.5 Abs and the deviation of the spectrum was corrected, the change in the peak intensity of the peak near the wave number 810 cm ^-1 in the inner surface of the protective film forming film (500) before and after ultraviolet irradiation was calculated by the following formula (1), and this was taken as the hardening rate of the inner surface of the protective film forming film in 500 mJ/cm ^2. Next, the ratio of the hardening rate of the inner surface of the protective film forming film in 500 mJ/cm ² to the hardening rate of the inner surface of the protective film forming film in 100 mJ/cm ² was calculated by the following formula (2), and this was taken as the hardening rate ratio of the protective film forming film.

Hardening rate = {(peak intensity before ultraviolet irradiation - peak intensity after ultraviolet irradiation)/peak intensity before ultraviolet irradiation} × 100 ・・・(1) Hardening rate ratio = (inner surface of protective film forming film at 500mJ/ Hardening rate in cm ² )/(hardening rate of the inner surface of the protective film forming film in 100mJ/cm ² )・・・(2)

The protective film forming film of this embodiment is a film used to provide a protective film on the inner surface of a chip to protect the chip.

By using the protective film-forming film of this embodiment or using the protective film-forming composite sheet provided with the protective film-forming film, a protective film-attached film having a wafer and a protective film provided on the inner surface of the wafer can be produced. wafer. The aforementioned wafer with a protective film can be produced by, for example, the following method: after attaching a protective film-forming film to the inner surface of the wafer, forming a protective film by curing the protective film-forming film, and dividing the wafer into wafers, Cut the protective film along the periphery of the wafer.

In this specification, examples include semiconductor wafers composed of element semiconductors such as silicon, germanium, and selenium or compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; semiconductor wafers composed of sapphire, glass, and lithium niobate. Insulator wafers composed of insulators such as lithium tantalate and lithium tantalate are used as "wafers". A circuit is formed on one surface of these wafers. In this specification, the surface of the wafer on which the circuit is formed is called a "circuit surface". Then, the surface of the wafer opposite to the circuit surface is called the "inner surface". The wafer is divided into chips by means such as dicing. In this specification, as in the case of a wafer, the surface of the wafer on the side on which the circuit is formed is called the "circuit surface", and the surface of the wafer opposite to the circuit surface is called the "inner surface". Protruding electrodes such as bumps and pillars are provided on both the circuit surface of the wafer and the circuit surface of the chip. The protruding electrode is preferably made of solder.

Furthermore, a substrate device can be manufactured by using the aforementioned chip with a protective film. In this specification, the so-called "substrate device" means a substrate device in which a chip with a protective film is flip-chip connected to a connection pad on a circuit substrate by a protruding electrode on a conductive surface. For example, as long as a semiconductor wafer is used as a wafer, a semiconductor device can be cited as a substrate device.

The protective film forming film of this embodiment is energy-ray curable, and furthermore, may be thermo-curable, or may not be thermo-curable. When the protective film forming film of this embodiment has both energy-ray curable and thermo-curable properties, the contribution of energy-ray curing of the protective film forming film to the formation of the protective film is greater than that of thermo-curing.

In this specification, the so-called "energy ray" means an energy ray with energy quanta in electromagnetic waves or charged particle beams. Examples of energy rays include ultraviolet rays, radiation, electron beams, etc. Ultraviolet rays can be irradiated by using 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 ray source. Electron beams are electron beams generated by electron beam accelerators, etc. In this specification, the so-called "energy ray curing" means the property of curing by irradiation with energy rays, and the so-called "non-energy ray curing" means the property of not curing even if irradiated with energy rays. Furthermore, the so-called "non-curing" means the property of not curing regardless of any means such as heating or irradiation with energy rays.

The curing conditions for forming a protective film by subjecting the protective film-forming film to energy ray curing are not particularly limited as long as the protective film has a degree of curing that fully exhibits the function of the protective film. The curing conditions may depend on the type of the protective film-forming film. Just choose appropriately. For example, the illumination intensity of the energy ray during energy ray curing of the energy ray curable protective film-forming film is preferably 60 mW/cm ² to 320 mW/cm ² . Furthermore, the light amount of the energy ray during the hardening is preferably 100 mJ/cm ² to 1000 mJ/cm ² .

The near-infrared transmittance of the protective film-forming film of this embodiment at a wavelength of 1300 nm is 10% or less. The near-infrared transmittance at a wavelength of 1300 nm can be measured, for example, using a commercially available ultraviolet/visible light/near-infrared spectrophotometer.

The near-infrared transmittance of the protective film-forming film of this embodiment at a wavelength of 1300nm is less than 10%. In order to make the near-infrared shielding effect more excellent, the near-infrared transmittance of the wavelength of 1300nm is preferably less than 8%, more preferably less than 6%, and further preferably less than 4%. The near-infrared transmittance of the protective film-forming film at a wavelength of 1300nm can also be more than 0.01%, more than 0.03%, more than 0.04%, and more than 0.1%. The near-infrared transmittance of the protective film-forming film of this embodiment at a wavelength of 365nm is preferably less than 0.20%, more preferably less than 0.18%, further preferably less than 0.17%, and particularly preferably less than 0.10% in order to make the near-infrared shielding effect more excellent. The near-infrared transmittance of the protective film-forming film at a wavelength of 365nm can also be above 0.005%, or above 0.008%.

The protective film-forming film of the present embodiment has a hardening rate ratio of 1.02 or more and less than 100 as measured by the hardening rate ratio measurement method described below.

<Method for measuring the curing rate ratio> The protective film forming film is irradiated with ultraviolet light from one side under the conditions of an illumination of 220 mW/ ^cm2 and a light quantity of 100 mJ/ ^cm2 to produce a protective film forming film (100) irradiated with ultraviolet light. The protective film forming film (100) before and after the ultraviolet light irradiation is subjected to FT-IR measurement at an incident angle of 45° and a diamond ATR method on the surface (inner surface) opposite to the surface irradiated with ultraviolet light of the protective film forming film (100) before and after the ultraviolet light irradiation. After the peak intensity of the peak near the wave number 790 cm ^-1 was normalized to 1.5 Abs and the deviation of the spectrum was corrected, the change in the peak intensity of the peak near the wave number 810 cm ^-1 on the inner surface of the protective film forming film (100) before and after the ultraviolet irradiation was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film in 100 mJ/cm ^2. Next, the protective film forming film (500) after ultraviolet irradiation was prepared in the same manner as above, except that the ultraviolet irradiation was performed under the conditions of 220 mW/cm ^{2 of illumination and 500 mJ/cm 2 of} light. The surface (inner surface) opposite to the surface irradiated with ultraviolet light in the protective film forming film (500) before and after the ultraviolet irradiation was subjected to FT-IR measurement under the same conditions as above. After the peak intensity of the peak near the wave number 790 cm ^-1 was normalized to 1.5 Abs and the deviation of the spectrum was corrected, the change in the peak intensity of the peak near the wave number 810 cm ^-1 in the inner surface of the protective film forming film (500) before and after ultraviolet irradiation was calculated by the following formula (1), and this was taken as the hardening rate of the inner surface of the protective film forming film in 500 mJ/cm ^2. Next, the ratio of the hardening rate of the inner surface of the protective film forming film in 500 mJ/cm ² to the hardening rate of the inner surface of the protective film forming film in 100 mJ/cm ² was calculated by the following formula (2), and this was taken as the hardening rate ratio of the protective film forming film.

Curing rate = {(peak intensity before UV irradiation - peak intensity after UV irradiation) / peak intensity before UV irradiation} × 100 ・・・(1) Curing rate ratio = (curing rate of the inner surface of the protective film forming film at 500mJ/ ^cm2 ) / (curing rate of the inner surface of the protective film forming film at 100mJ/ ^cm2 ) ・・・(2)

By setting the curing rate ratio calculated by equation (2) to be 1.02 or more, when the protective film-forming film is subjected to energy ray hardening, the degree of curing of the protective film-forming film is set to an appropriate range, thereby improving the performance of the protective film and The adhesion of the silicon wafer prevents the protective film from easily peeling off.

Since the curing rate ratio calculated by the formula (2) is less than 100, when the protective film-forming film is subjected to energy beam hardening, the degree of curing of the protective film-forming film is set to an appropriate range, thereby improving the protective film. The adhesion to the silicon wafer prevents the protective film from easily peeling off.

In the protective film forming film of the present embodiment, the hardening rate ratio obtained by formula (2) is greater than 1.02. In order to improve the adhesion between the protective film and the silicon wafer and more appropriately prevent the protective film from peeling off, the hardening rate ratio obtained by formula (2) is preferably greater than 1.1, more preferably greater than 2.0, and further preferably greater than 2.5.

In the protective film forming film of the present embodiment, the hardening rate ratio obtained by formula (2) is less than 100. In order to improve the adhesion between the protective film and the silicon wafer and more appropriately prevent the protective film from peeling off, it is preferably less than 50, more preferably less than 20, further preferably less than 15, particularly preferably less than 10, and most preferably less than 5.

In the protective film forming film of the present embodiment, in order to improve the adhesion between the protective film and the silicon wafer and to more appropriately prevent the protective film from peeling off, the hardening rate of the inner surface of the protective film forming film obtained by formula (1) at 100mJ/ ^cm2 is preferably 0.1% or more, more preferably 0.5% or more, further preferably 0.8% or more, and particularly preferably 1.0% or more. Furthermore, in the protective film forming film of the present embodiment, in order to improve the adhesion between the protective film and the silicon wafer and to more appropriately prevent the protective film from peeling off, the hardening rate of the inner surface of the protective film forming film obtained by formula (1) at 100mJ/ ^cm2 is preferably 79% or less, more preferably 75% or less, further preferably 70% or less, particularly preferably 30% or less, and most preferably 25% or less.

In the protective film-forming film of this embodiment, in order to improve the adhesion between the protective film and the silicon wafer and more appropriately prevent the peeling of the protective film, the inner surface of the protective film-forming film obtained by the formula (1) is heated to 500 mJ The hardening rate per cm ² is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more. Furthermore, in the protective film-forming film of this embodiment, in order to improve the adhesion between the protective film and the silicon wafer and more appropriately prevent the peeling of the protective film, within the protective film-forming film obtained by the formula (1) The hardening rate within 500 mJ/cm ² is preferably 90% or less, more preferably 85% or less, further preferably 80% or less, particularly preferably 75% or less, and most preferably 70% or less.

Examples of the protective film forming film include an acrylic resin (b) containing an energy ray curable component (a) and not having an energy ray curable group. The components contained in the protective film-forming film will be described in detail later.

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

In this specification, not limited to the case of a protective film forming film, the phrase "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some layers may be the same", and the phrase "multiple layers may be different from each other" means "at least one of the constituent material and thickness of each layer is different from each other".

The thickness of the protective film forming film is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm, and particularly preferably 5 μm to 60 μm. By making the thickness of the protective film forming film above the aforementioned lower limit, a protective film with higher protective ability can be formed. By making the thickness of the protective film forming film below the aforementioned upper limit, the thickness of the chip with the protective film can be prevented from becoming too thick. Here, the so-called "thickness of the protective film forming film" means the thickness of the protective film forming film as a whole. For example, the so-called thickness of the protective film forming film of a multi-layer structure means the total thickness of all layers constituting the protective film forming film. The "thickness" in this manual can be obtained by the method specified in JIS K 7130: 1999 (ISO 4593: 1993).

＜＜Composition for protective film formation＞＞ The protective film-forming film can be formed using an energy-beam-curable protective film-forming composition (hereinafter, sometimes referred to only as "protective film-forming composition") containing a constituent material of the protective film-forming film. For example, the protective film-forming film can be formed by applying the protective film-forming composition to a surface to be formed of the protective film-forming film and drying it if necessary. The content ratio of components that do not vaporize at normal temperature in the protective film-forming composition is usually the same as the content ratio of the aforementioned components in the protective film-forming film. In this specification, "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, an ordinary temperature. Examples thereof include a temperature of 18°C to 28°C.

The coating of the protective film forming composition can be carried out by a known method, for example, a method using the following various coaters: air knife coater, doctor blade coater, rod coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Mayer bar coater, touch coater, etc.

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

<Energy ray curable protective film forming composition (IV)> Preferred protective film forming compositions include, for example, a composition containing the energy ray curable component (a), the acrylic resin (b) having no energy ray curable group, and the inorganic filler (d). Composition (IV) for forming an energy-beam curable protective film (herein, may only be referred to as "composition (IV)"), etc.

[Energy ray curing component (a)] The energy ray curing component (a) is a component that is cured by irradiating energy rays, and is also a component used to impart film-forming properties or flexibility to the protective film-forming film, and to form a hard protective film after curing. The protective film-forming film is a protective film with good properties formed by containing the energy ray curing component (a). In the protective film-forming film, the energy ray curing component (a) is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.

Examples of the energy ray-curable component (a) include 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 (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000. The polymer (a1) may be at least partially crosslinked by a crosslinking agent or may not be crosslinked.

(Polymer (a1) having an energy ray hardening group and a weight average molecular weight of 80,000 to 2,000,000) Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) (having a functional group capable of reacting with a group possessed by other compounds) and an energy ray. Acrylic resin (a1-1) obtained by reacting a curable compound (a12) (having an energy ray curable group such as a group that reacts with the functional group and an energy ray curable double bond).

Examples of the functional group that can react with a group possessed by other compounds include: hydroxyl group, carboxyl group, amino group, substituted amino group (a group having a structure in which one or two hydrogen atoms of an amino group are replaced by a group other than a hydrogen atom), epoxy group, etc. However, in terms of preventing corrosion of circuits such as wafers or chips, the functional group is preferably a group other than a carboxyl group. Among these functional groups, the functional group is preferably a hydroxyl group.

・Acrylic polymer (a11) having a functional group Examples of the acrylic polymer (a11) having a functional group include an acrylic polymer obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer not having the functional group, and an acrylic polymer obtained by copolymerizing these monomers with a monomer other than the acrylic monomer (non-acrylic monomer). The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may be used for the polymerization method.

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

Examples of the hydroxyl-containing monomer include: (hydroxymethylmeth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates; vinyl alcohol , non-(meth)acrylyl unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acrylyl skeleton), etc.

Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) 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. Carboxyalkyl (meth)acrylate, etc.

The aforementioned acrylic monomer with functional groups is preferably a hydroxyl-containing monomer.

The acrylic monomers having functional groups constituting the acrylic polymer (a11) may be only one type, or may be two or more types. When there are two or more types, the combination and ratio of those acrylic monomers can be selected arbitrarily. .

Examples of the acrylic monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, Alkyl esters such as 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 (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc., wherein the alkyl group constituting the alkyl ester is a chain structure having 1 to 18 carbon atoms.

Furthermore, examples of the aforementioned acrylic monomers having no functional groups include: (meth)acrylates containing alkoxyalkyl groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; (meth)acrylates containing aromatic groups such as aryl (meth)acrylates including phenyl (meth)acrylate; non-crosslinking (meth)acrylamide and its derivatives; (meth)acrylates containing non-crosslinking tertiary amine groups such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate, and the like.

The acrylic monomers without functional groups constituting the acrylic polymer (a11) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of those acrylic monomers can be arbitrary. select.

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

In the acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having a functional group to the total amount of structural units constituting the acrylic polymer (a11) is preferably 0.1. mass% to 50 mass%, more preferably 1 mass% to 40 mass%, particularly preferably 3 mass% to 30 mass%. When the aforementioned ratio is in such a range, the content of the energy ray curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12) is It can adjust the hardening degree of the protective film to a better range.

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

In the protective film-forming film, the content of the acrylic resin (a1-1) relative to the total mass of the protective film-forming film is preferably 1 mass % to 70 mass %, more preferably 5 mass % to 60 mass %, particularly Preferably, it is 10 mass % to 50 mass %.

・Energy ray curing compound (a12) The energy ray curing compound (a12) preferably has one or more selected from the group consisting of isocyanate group, epoxy group and carboxyl group as a group capable of reacting with the functional group possessed by the acrylic polymer (a11), and more preferably has an isocyanate group as the aforementioned group. When the energy ray curing compound (a12) has an isocyanate group as the aforementioned group, for example, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the aforementioned functional group.

The number of the energy ray curable groups contained in one molecule of the energy ray curable compound (a12) is not particularly limited, and can be appropriately selected in consideration of physical properties such as shrinkage rate required for the target protective film. For example, the energy ray curable compound (a12) preferably has 1 to 5 of the energy ray curable groups per 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 methacrylyl isocyanate. isocyanate, allyl isocyanate, 1,1-(bisacrylyloxymethyl)ethyl isocyanate; produced by the reaction of a diisocyanate compound or a polyisocyanate compound and hydroxyethyl (meth)acrylate Acrylyl monoisocyanate compound obtained; acrylyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth)acrylate, etc. Among these, the energy ray curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The energy ray curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types. In the case of two or more types, those energy ray curable compounds (a12) Combinations and ratios can be selected 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%. When the ratio of the aforementioned content is within such a range, the adhesive force of the cured material of the protective film-forming film becomes greater. In addition, when the energy ray curable compound (a12) is a monofunctional (having one of the above groups in one molecule) compound, the upper limit of the content ratio is 100 mol%. However, when the energy ray curable compound (a12) is When the sexual compound (a12) is a polyfunctional (having two or more of the above-mentioned groups in one molecule) compound, the upper limit of the above-mentioned content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000.

In this specification, the so-called "weight average molecular weight" is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) unless otherwise specified.

The composition (IV) and the protective film-forming film may contain only one type of the above-mentioned polymer (a1) or two or more types. When two or more types are contained, the combination and ratio of the polymers (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 the compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000, a group containing an energy ray curable double bond can be cited, and as preferred aforementioned energy ray curable groups, (meth)acryl group, vinyl group, etc. can be cited.

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

Examples of the acrylate compound include polyfunctional monomers or oligomers, and a polyfunctional acrylate compound having two or more (meth)acrylyl groups per molecule is preferred. . Examples of the polyfunctional acrylate compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated Ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate (Meth)acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)propene Cyloxyethoxy)phenyl]fluoride, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylic acid Ester (alias: tricyclodecane dimethylol 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, polybutylene glycol Di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4 -((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1 , 2-functional (meth)acrylate such as 3-di(meth)acryloxypropane ((meth)acrylate having two (meth)acrylyl groups in one molecule); isocyanuride Tris(2-(meth)acryloxyethyl) acid, ε-caprolactone denatured isocyanurate tris-(2-(meth)acryloxyethyl) ester, ethoxylation Glyceryl tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated Pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other multifunctional (meth)acrylates (1 molecule (meth)acrylate with more than 3 (meth)acrylyl groups); multifunctional (meth)acrylate oligomer such as multifunctional (meth)acrylic urethane oligomer ((meth)acrylate oligomer having two or more (meth)acrylyl groups in one molecule), etc.

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

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) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of those compounds (a2) can be Choose arbitrarily.

The protective film-forming film preferably contains the aforementioned compound (a2), more preferably contains a multifunctional acrylate compound having two or more (meth)acryl groups in one molecule, and further preferably contains a multifunctional (meth)acrylic urethane oligomer as the energy ray-curable component (a). The protective film-forming film containing such an energy ray-curable component (a) has a good protective ability and is also flexible, and has particularly excellent characteristics.

When the composition (IV) and the protective film-forming film contain the energy ray curable component (a), the energy ray curable component (a) is contained in the composition (IV) and the protective film-forming film relative to 100 parts by mass of the acrylic resin (b). The content of the sexual component (a) is preferably from 100 parts by mass to 310 parts by mass, more preferably from 130 parts by mass to 280 parts by mass, for example, it may be 130 parts by mass to 200 parts by mass, or 210 parts by mass to 280 parts by mass. share.

In the composition (IV), the content ratio of the energy ray curable component (a) relative to the total content of all components other than the solvent (that is, the content ratio of the energy ray curable component (a) relative to the total mass of the protective film forming film in the protective film forming film) is preferably 12 mass % to 31 mass %, more preferably 14 mass % to 28 mass %, and more preferably 16 mass % to 25 mass %. When the content ratio of the energy ray curable component (a) (that is, the content ratio of the energy ray curable component (a)) is above the aforementioned lower limit, the energy ray curability of the aforementioned protective film forming film becomes better. When the content ratio of the energy ray curable component (a) (that is, the content ratio of the energy ray curable component (a)) is below the aforementioned upper limit, it is easy to prepare the desired protective film forming film.

[Acrylic resin (b) without energy ray curable group] The protective film-forming film preferably contains an acrylic resin (b) that does not have an energy ray curable group (in this specification, it may be simply referred to as "acrylic resin (b)").

The acrylic resin (b) is a component that imparts film-forming properties to the protective film-forming film.

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

The acrylic resin (b) preferably has a structural unit derived from 4-(meth)acrylylmorpholine. That is, the acrylic resin (b) is preferably a polymer of 4-(meth)acrylmorpholine. Since the acrylic resin (b) has a structural unit derived from 4-(meth)acryloylmorpholine, the acrylic resin (b) has excellent adhesion to the above-mentioned wafer or wafer, and the protective film is formed from the wafer. Or the effect of inhibiting wafer peeling becomes higher.

The acrylic resin (b) preferably has a constituent unit derived from 4-(meth)acryloylmorpholine and a constituent unit other than the constituent unit derived from 4-(meth)acryloylmorpholine. That is, the acrylic resin (b) is preferably a copolymer of 4-(meth)acryloylmorpholine and a monomer or oligomer other than the constituent unit derived from 4-(meth)acryloylmorpholine.

In the acrylic resin (b), the ratio of the amount of the constituent units derived from 4-(meth)acryloylmorpholine to the total amount of the constituent units is preferably 10 to 30 mass%, more preferably 13 to 30 mass%, and may be any one of 18 to 30 mass%, and 23 to 30 mass%.

The acrylic resin (b) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.

Examples of the acrylic monomers constituting the acrylic resin (b) include (meth)acrylates such as alkyl (meth)acrylates, (meth)acrylates having no functional group but having a cyclic skeleton, (meth)acrylates containing a glycidyl group, (meth)acrylates containing a hydroxyl group, (meth)acrylates containing a substituted amino group, (meth)acrylates containing a carboxyl group, and (meth)acrylates containing an amino group; (meth)acrylamide; (meth)acrylamide derivatives such as 4-(meth)acryloylmorpholine, etc. Here, the so-called "substituted amino group" means a group having a structure in which one or two hydrogen atoms of an amino group are replaced by a group other than a hydrogen atom. Here, the so-called "functional group" means a group (reactive functional group) that can react with other groups such as a glycidyl group, a hydroxyl group, a substituted amino group, a carboxyl group, and an amino group.

In this specification, "(meth)acrylic acid" includes the concept of both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, the so-called "(meth)acrylate" includes the concepts of both "acrylate" and "methacrylate", and the so-called "(meth)acrylyl" It is a concept that includes both "acrylyl" and "methacrylyl".

In this specification, assuming that a specific compound has a structure in which one or more hydrogen atoms are substituted by a group other than a hydrogen atom, the compound having such a substituted structure is referred to as "the above-mentioned specific compound" derivative". In this specification, the so-called "group" includes not only an atomic group in which a plurality of atoms are bonded, but also a single atom.

Examples of the alkyl (meth)acrylate that does not have a functional group or a cyclic skeleton include: (methyl)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylate Isopropyl methacrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, (meth) Amyl acrylate, hexyl (meth)acrylate, 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 ((meth)acrylate (Basic) Lauryl acrylate), Tridecyl (meth)acrylate, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Cetyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate) ), etc. The alkyl group constituting the alkyl ester is a (meth)acrylic acid alkyl ester with a chain structure having a carbon number of 1 to 18.

Examples of the aforementioned (meth)acrylate having no functional group but having a cyclic skeleton include: cycloalkyl (meth)acrylates such as isoborneol (meth)acrylate and dicyclopentanyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; cycloolefin (meth)acrylates such as dicyclopentenyl (meth)acrylate; cycloolefin (meth)acrylates such as dicyclopentenyl (meth)acrylate; and cycloolefinoxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate.

Examples of the aforementioned glycidyl-containing (meth)acrylate include glycidyl (meth)acrylate. Examples of the aforementioned hydroxyl-containing (meth)acrylate include: a structure in which one or more hydrogen atoms are replaced by hydroxyl groups in one of the aforementioned (meth)acrylate alkyl esters without functional groups and cyclic skeletons and the aforementioned (meth)acrylates without functional groups but with cyclic skeletons. Examples of preferred aforementioned hydroxyl-containing (meth)acrylates include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the aforementioned (meth)acrylate containing a substituted amino group include N-methylaminoethyl (meth)acrylate, etc.

Examples of the non-acrylic monomers constituting the acrylic resin (b) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

As an acrylic resin (b) at least partly crosslinked by a crosslinking agent, for example, a functional group in the acrylic resin (b) reacts with a crosslinking agent. The functional group is not particularly limited as long as it is appropriately selected according to the type of the crosslinking agent. For example, when the crosslinking agent is a polyisocyanate compound, as the functional group, hydroxyl, carboxyl, amine, etc. can be cited, and among these functional groups, hydroxyl groups with high reactivity with isocyanate groups are preferred. Furthermore, when the crosslinking agent is an epoxy compound, as the functional group, carboxyl, amine, etc. can be cited, and among these functional groups, carboxyl groups with high reactivity with epoxy groups are preferred. However, in terms of preventing corrosion of the circuits of wafers or chips, the aforementioned functional groups are preferably groups other than carboxyl groups.

As the aforementioned acrylic resin (b) having a functional group, for example, there can be cited an acrylic resin obtained by polymerizing at least the aforementioned monomer having a functional group. As the aforementioned acrylic resin (b) having a functional group, more specifically, for example, there can be cited an acrylic resin obtained by polymerizing one or more monomers selected from the group consisting of the aforementioned glycidyl-containing (meth)acrylate, the aforementioned hydroxyl-containing (meth)acrylate, the aforementioned substituted amino-containing (meth)acrylate, the aforementioned carboxyl-containing (meth)acrylate, the aforementioned amino-containing (meth)acrylate, and the aforementioned non-acrylic monomer having a structure in which one or more hydrogen atoms are substituted by the aforementioned functional group.

In the acrylic resin (b), the proportion (content) of the amount of structural units derived from the monomer having a functional group relative to the total amount of the structural units constituting the acrylic resin (b) is preferably 1 to 20% by mass. mass %, more preferably 2 mass % to 10 mass %. When the aforementioned ratio is within such a range, the degree of crosslinking in the acrylic resin (b) becomes a more optimal range.

The weight average molecular weight (Mw) of the acrylic resin (b) is preferably 10,000 or more, more preferably 20,000 or more, and still more preferably 40,000 or more, in order to further suppress bleeding due to the reflux step. The weight average molecular weight (Mw) of the acrylic resin (b) is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, in view of the film-forming property of the composition (IV) becoming better.

The acrylic resin (b) contained in the composition (IV) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of those acrylic resins (b) Can choose arbitrarily.

In the composition (IV), the ratio of the content of the acrylic resin (b) to the total content of all components except the solvent (that is, in the protective film-forming film, the content of the acrylic resin (b) in the protective film-forming film is The proportion of the total mass) is preferably 8 mass% or more, more preferably 10 mass% or more, for example, it may be any one of 12 mass% or more and 14 mass% or more.

In the composition (IV), the ratio of the content of the acrylic resin (b) to the total content of all components except the solvent (that is, in the protective film-forming film, the content of the acrylic resin (b) in the protective film-forming film is The upper limit of the proportion of the total mass) is not particularly limited. The upper limit may be 27% by mass or less, preferably 25% by mass or less, in that the protective film exhibits a good balance between the characteristics of suppressing bleedout due to the reflow step and characteristics other than these characteristics. , more preferably 23% by mass or less, still more preferably 21% by mass or less.

In composition (IV), the ratio of the content of acrylic resin (b) to the total content of all components other than the solvent (i.e., the ratio of the content of acrylic resin (b) to the total mass of the protective film forming film in the protective film forming film) can be appropriately adjusted within the range set by any combination of the lower limit and the upper limit of any of the above. For example, in one embodiment, the above ratio is preferably 8% by mass to 27% by mass, more preferably 10% by mass to 25% by mass, and can also be any one of 12% by mass to 23% by mass, and 14% by mass to 21% by mass.

When the composition (IV) and the protective film-forming film contain the energy ray curable component (a) and the acrylic resin (b), the content of the composition (IV) and the protective film-forming film relative to the acrylic resin (b) is 100 In parts by mass, the content of the energy ray hardening component (a) is preferably 70 to 310 parts by mass, more preferably 80 to 280 parts by mass, and more preferably 85 to 250 parts by mass.

In the composition (IV), the ratio of the total content of the energy ray curable component (a) and the acrylic resin (b) to the total content of all components other than the solvent (i.e., the ratio of the total content of the energy ray curable component (a) and the acrylic resin (b) to the total mass of the protective film forming film) is preferably 10% by mass to 60% by mass, for example, it may be any one of 20% by mass to 50% by mass and 30% by mass to 45% by mass. When the above ratio is within such a range, the effect brought about by using the energy ray curable component (a) and the acrylic resin (b) becomes higher.

[Other ingredients] The composition (IV) and the protective film-forming film may contain other components that are not equivalent to either the energy ray curable component (a) or the acrylic resin (b) within the range that does not impair the effects of the present invention. . Examples of the aforementioned other components include: photopolymerization initiator (c); inorganic filler (d); coupling agent (e); cross-linking agent (f); colorant (g); thermosetting component ( h); general additive (z); polymer (b0) not equivalent to acrylic resin (b) and not having an energy ray curable group (in this specification, it is sometimes referred to as "other polymers not having an energy ray curable group"). "Polymer (b0)" or "Polymer (b0)"), etc.

(Photopolymerization initiator (c)) When the composition (IV) and the protective film-forming film contain the photopolymerization initiator (c), the polymerization (hardening) reaction of the energy ray curable component (a) proceeds efficiently.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2 -Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanyl)benzyl)phenyl)-2-methylpropan-1-one, 2-(dimethylamino) -Acetophenone compounds such as 1-(4-morpholinylphenyl)-2-benzyl-1-butanone; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other acylphosphine oxide compounds; benzylphenyl sulfide, tetramethylthiuram monosulfide and other sulfide compounds; 1-hydroxyl α-ketool compounds such as cyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; Diketone compounds such as diethyl chloride; benzoyl chloride; diphenyl chloride; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl Base-1-[4-(1-methylvinyl)phenyl]acetone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone. Examples of the photopolymerization initiator include photosensitizers such as amines.

The photopolymerization initiator (c) contained in the composition (IV) and the protective film-forming film may be only one type, or two or more types. In the case of two or more types, those photopolymerization initiators (c) ) combinations and ratios can be selected arbitrarily. For example, highly reactive photopolymerization initiators, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, which are liquid at room temperature, can efficiently exchange protective film-forming films when used alone. Connection can increase the gel fraction. 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropyl)benzyl)phenyl)-2-methylpropan-1-one, 1-hydroxycyclohexyl-phenyl Photopolymerization initiators with low reactivity such as ketones are produced by reaction with 2-(dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone, etc. The combined use of a highly photopolymerization initiator can effectively cross-link the protective film-forming film and increase the gel fraction.

When a photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the composition (IV) is preferably 0.1 parts by mass relative to 100 parts by mass of the energy ray curable component (a). part to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.

(Inorganic filler (d)) When the composition (IV) and the protective film-forming film contain the inorganic filler (d), the protection can be adjusted more easily by adjusting the amount of the inorganic filler (d) in the composition (IV) and the protective film-forming film. The thermal expansion coefficient of a cured product of a film-forming film (for example, a protective film). For example, by optimizing the thermal expansion coefficient of the protective film for the object on which the protective film is formed, the reliability of the package obtained using the protective film forming film will be further improved. Furthermore, by using the protective film-forming film containing the inorganic filler (d), the moisture absorption rate of the cured product of the protective film-forming film (eg, protective film) can also be reduced, or the heat dissipation property can be improved.

Examples of inorganic fillers (d) include: powders of inorganic materials such as silica, alumina, talc, calcium carbonate, titanium dioxide, red iron, silicon carbide, and boron nitride; beads obtained by spheronizing these inorganic materials; surface-modified products of these inorganic materials; single-crystal fibers of these inorganic materials; and glass fibers. Furthermore, surface-modified products include methoxy-modified, epoxy-modified, and phenyl-modified products. Among these inorganic materials, the inorganic filler (d) is preferably silica or alumina.

The inorganic filler (d) contained in the composition (IV) and the protective film-forming film may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the inorganic fillers (d) can be arbitrarily selected.

In the composition (IV), the ratio of the content of the inorganic filler (d) to the total content of all components except the solvent (that is, in the protective film-forming film, the content of the inorganic filler (d) to the protective film The proportion of the total mass of the film formed) is preferably 35 mass% to 75 mass%, and may be any one of 45 mass% to 70 mass%, and 50 mass% to 65 mass%. By keeping the aforementioned ratio in such a range, the film-forming properties of the protective film are not impaired, and the efficiency of using the inorganic filler (d) becomes higher.

(Coupling agent (e)) When the composition (IV) and the protective film-forming film contain the coupling agent (e) (having a functional group capable of reacting with an inorganic compound or an organic compound), the adhesiveness and adhesion of the protective film-forming film to the adherend will be improved. . Furthermore, the cured product of the protective film-forming film (such as a protective film) does not impair the heat resistance and improves the water resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group possessed by the acrylic resin (b), the energy ray curable component (a), etc., and is more preferably a silane coupling agent. Preferable examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane. Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, Vinyltrimethoxysilane, vinyltriacetyloxysilane, imidazolesilane, etc.

The coupling agent (e) contained in the composition (IV) and the protective film-forming film may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the coupling agents (e) can be arbitrarily selected.

When a coupling agent (e) is used, the content of the coupling agent (e) in the composition (IV) and the protective film-forming film is preferably 0.03 to 20 parts by mass relative to 100 parts by mass of the total content of the energy ray-curable component (a) and the acrylic resin (b). When the content of the coupling agent (e) is above the lower limit, the effects of the coupling agent (e), such as improving the dispersibility of the inorganic filler (d) in the resin or improving the adhesion between the protective film-forming film and the adherend, can be more significantly obtained. When the content of the coupling agent (e) is below the upper limit, the occurrence of outgassing can be further suppressed.

(Crosslinking agent (f)) When a compound having a functional group such as a vinyl group, (meth)acryl group, amine group, hydroxyl group, carboxyl group, isocyanate group, etc. that can be bonded to other compounds is used as the acrylic resin (b), the composition (IV) The protective film-forming film may also contain a cross-linking agent (f). The cross-linking agent (f) is a component for cross-linking the aforementioned functional group in the acrylic resin (b) by bonding it to other compounds. By cross-linking in this way, the initial adhesive force of the protective film-forming film can be adjusted. and cohesion.

Examples of the crosslinking agent (f) include organic polyisocyanate compounds, organic polyimide compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridine group), and the like.

Examples of the aforementioned organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds are sometimes collectively referred to as "aromatic polyisocyanate compounds, etc."); trimers, isocyanurates, and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds, etc. The aforementioned "adduct" refers to the reaction product of the aforementioned aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, or alicyclic polyisocyanate compounds with a compound containing low molecular weight active hydrogen, such as ethylene glycol, propylene glycol, neopentyl glycol, trihydroxymethylpropane, or castor oil. Examples of the adduct include the trihydroxymethylpropane xylylene diisocyanate adduct described below. In addition, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.

More specifically, the organic polyisocyanate compound includes: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-phenylenedimethyl diisocyanate; 1,4-phenylenedimethyl diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethoxybenzene; Methyl diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; a compound obtained by adding any one or two or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate to all or part of the hydroxyl groups of a polyol such as trihydroxymethylpropane; lysine diisocyanate, etc.

Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinemethane), trimethylolpropane-tri-β- Aziriridinyl propionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinylmethamide)trisexanide Ethylmelamine, etc.

When an organic polyisocyanate compound is used as the cross-linking agent (f), it is preferable to use a hydroxyl-containing polymer as the acrylic resin (b). When the cross-linking agent (f) has an isocyanate group and the acrylic resin (b) has a hydroxyl group, the cross-linked structure can be easily introduced into the protective film through the reaction between the cross-linking agent (f) and the acrylic resin (b). Form a film.

The composition (IV) and the protective film-forming film may contain only one crosslinking agent (f) or two or more crosslinking agents. When there are two or more crosslinking agents (f), the combination and ratio of the crosslinking agents (f) can be arbitrarily selected.

When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the composition (IV) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the acrylic resin (b). By setting the aforementioned content of the cross-linking agent (f) above the aforementioned lower limit, the effects brought about by the use of the cross-linking agent (f) can be more significantly obtained. By setting the content of the cross-linking agent (f) below the upper limit, excessive use of the cross-linking agent (f) can be suppressed.

(Color(g)) The composition (IV) and the protective film-forming film preferably contain an inorganic pigment as the colorant (g). By adjusting the content of the inorganic pigment, the transmittance of the near-infrared rays of the protective film-forming film, especially the near-infrared rays with a wavelength of 1300 nm, can be adjusted.

Examples of the inorganic pigments include carbon black, titanium black, zirconium nitride, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (Indium Tin Oxide; indium tin oxide) pigments, ATO (Antimony Tin Oxide; antimony tin oxide) pigments, etc. Among these inorganic pigments, carbon black, titanium black, and zirconium nitride are preferred, and a combination of carbon black and titanium black is particularly preferred. Carbon black is inexpensive, and titanium black is less likely to reduce the energy ray hardening property of the protective film formation film. Furthermore, zirconium nitride is less likely to increase the heat storage property of the protective film forming film and the protective film forming layer than carbon black, and thus can prevent shrinkage due to heat during energy ray curing.

The content of the composition (IV) and the inorganic pigment forming the protective film may be appropriately adjusted so that the transmittance of near-infrared rays with a wavelength of 1300 nm becomes appropriate. For example, in the composition (IV), the content of the colorant (g) is in proportion to the total content of all components except the solvent (that is, in the protective film-forming film, the content of the colorant (g) is The proportion of the total mass of the film forming film) is preferably 0.05 mass% or more and less than 5 mass%, more preferably 0.05 mass% to 4 mass%, and particularly preferably 0.1 mass% to 3 mass%. When the aforementioned ratio is equal to or higher than the aforementioned lower limit, the effects brought about by the use of the coloring agent (g) can be more significantly obtained. When the ratio is equal to or less than the upper limit, excessive use of the colorant (g) can be suppressed. Furthermore, by using a plurality of colorants together, it becomes easy to adjust the transmittance of each wavelength, and the cost balance can be improved.

As the colorant (g), in addition to inorganic pigments, known colorants such as organic pigments and organic dyes may also be included. Examples of the organic pigments and organic dyes include amine-based pigments, cyanine-based pigments, merocyanin-based pigments, ketonium-based pigments, squarylium-based pigments, azulium-based pigments, and polyanium-based pigments. Methine pigments, naphthoquinone pigments, pyranium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, Iconone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinolinphthalone pigments, pyrrole pigments, thioindigo pigments, metal complexes Physical pigments (metal complex dyes), dithiol metal complex pigments, indophenol pigments, triarylmethane pigments, anthraquinone pigments, naphthol pigments, methimine pigments, benzo Imidazolone pigments, picanthrone pigments and Shilin pigments, etc.

Furthermore, by adjusting the content of the colorant (g), it is possible to adjust the visibility of the laser mark when laser marking is performed on the protective film forming film or the protective film, for example. In addition, the design of the protective film can be improved, or the grinding marks on the inner surface of the wafer can be made less visible.

The colorant (g) contained in the composition (IV) and the protective film-forming film may be only one type or two or more types. In the case of two or more types, the combination and ratio of the coloring agents (g) can be Choose arbitrarily.

(Thermosetting component (h)) When the composition (IV) and the protective film forming film contain the energy ray-curing component (a) and the thermosetting component (h), the protective film forming film improves the adhesion to the adherend by heating, and the strength of the cured product of the protective film forming film (such as the protective film) is also improved.

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

The aforementioned epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2). The epoxy-based thermosetting resin contained in the composition (IV) and the protective film-forming film may be only one type or two or more types. When there are two or more types, the combination and ratio of those epoxy-based thermosetting resins can be arbitrarily selected.

・Epoxy resin (h1) Examples of the epoxy resin (h1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolak rings. Oxygen resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Two or more functional rings oxygen compounds.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The mutual solubility of epoxy resins with unsaturated hydrocarbon groups and acrylic resins is higher than that of epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a wafer with a protective film obtained using a composite sheet for forming a protective film is improved.

Examples of epoxy resins having unsaturated hydrocarbon groups include compounds in which a part of epoxy groups in a multifunctional epoxy resin is converted into groups having unsaturated hydrocarbon groups. Such compounds can be obtained, for example, by subjecting (meth)acrylic acid or a derivative of (meth)acrylic acid to an addition reaction of epoxy groups. In addition, examples of epoxy resins having unsaturated hydrocarbon groups include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include: ethylene (vinyl), 2-propenyl (allyl), (meth)acryl, (meth)acrylamide, etc., preferably acryl.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but in terms of the curability of the protective film-forming film, and the strength and heat resistance of the protective film, 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 (h1) is preferably 100 g/eq to 1,000 g/eq, and more preferably 150 g/eq to 950 g/eq.

The epoxy resin (h1) contained in the composition (IV) and the protective film-forming film may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of those epoxy resins (h1) can be arbitrarily selected.

・Thermosetting agent (h2) Thermosetting agent (h2) functions as a hardener for epoxy resin (h1). As the thermosetting agent (h2), for example, there can be cited: a compound having two or more functional groups that can react with an epoxy group in one molecule. As the functional group, for example, there can be cited: a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by anhydriding an acid group, etc., preferably a phenolic hydroxyl group, an amino group, or a group formed by anhydriding an acid group, and more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of phenolic curing agents having a phenolic hydroxyl group include: multifunctional phenol resins, biphenol, novolac-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl-type phenol resins, etc. Among the thermosetting agents (h2), examples of amine-based curing agents having an amine group include dicyandiamide, etc.

Thermosetting agent (h2) may also have an unsaturated hydrocarbon group. Examples of thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound having a structure in which a part of the hydroxyl groups of a phenol resin is replaced by a group having an unsaturated hydrocarbon group, and a compound having a structure in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of a phenol resin. Examples of the unsaturated hydrocarbon group in thermosetting agent (h2) include the same unsaturated hydrocarbon group as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

When a phenol-based hardener is used as the thermosetting agent (h2), the thermosetting agent (h2) preferably has a high softening point or glass transition temperature in terms of improving the peelability of the self-supporting sheet of the protective film.

The number average molecular weight of the resin components in the thermosetting agent (h2), such as multifunctional phenol resin, novolac phenol resin, dicyclopentadiene phenol resin, aralkyl phenol resin, etc., is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. The molecular weight of the non-resin components in the thermosetting agent (h2), such as diphenol, dicyandiamide, etc., is not particularly limited, and is preferably 60 to 500, for example.

The thermosetting agent (h2) contained in the composition (IV) and the protective film-forming film may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of those thermosetting agents (h2) can be selected arbitrarily.

When a thermosetting component (h) is used, the content of the thermosetting agent (h2) in the composition (IV) and the protective film-forming film is preferably 0.1 with respect to 100 parts by mass of the epoxy resin (h1). parts by mass to 100 parts by mass. When the content of the thermosetting agent (h2) is equal to or higher than the lower limit, the protective film-forming film can be cured more easily. When the content of the thermosetting agent (h2) is below the upper limit, the moisture absorption rate of the protective film-forming film is reduced, and the reliability of the package obtained using the wafer with a protective film is further improved.

When a thermosetting component (h) is used, the content of the thermosetting component (h) (for example, ring The total content of the oxygen resin (h1) and the thermosetting agent (h2) is preferably 5 to 120 parts by mass. When the aforementioned content of the thermosetting component (h) is within such a range, for example, the adhesive force between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability of the support sheet is improved.

(General Additive(z)) The general-purpose additive (z) can be a publicly known additive and can be selected arbitrarily according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives (z) include plasticizers, antistatic agents, antioxidants, gettering agents, and ultraviolet absorbers.

The general additive (z) contained in the composition (IV) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of those general additives (z) can Choose arbitrarily.

When a general additive (z) is used, the content of the general additive (z) in the composition (IV) and the protective film-forming film is not particularly limited and can be appropriately selected according to the purpose. For example, when the general additive (z) is a UV absorber, the content of the general additive (z) (UV absorber) in the composition (IV) is preferably 0.1 mass % to 5 mass % relative to the total content of all components other than the solvent (that is, in the protective film-forming film, the content of the general additive (z) (UV absorber) relative to the total mass of the protective film-forming film). By making the above ratio above the above lower limit, the effect brought about by the use of the general additive (z) can be more significantly obtained. By making the above ratio below the above upper limit, excessive use of the general additive (z) can be suppressed.

(Other polymers (b0) without energy ray hardening groups) The other polymer (b0) which does not have an energy ray curable group imparts film-forming properties to the protective film-forming film. The polymer (b0) is not particularly limited as long as it does not correspond to the acrylic resin (b). The polymer (b0) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.

Examples of the polymer (b0) include acrylic resins having a weight average molecular weight exceeding 1,100,000, acrylic resins having a dispersity of 3.0 or less (these acrylic resins are sometimes referred to as "other acrylic resins" in this specification); polymers other than acrylic resins having no energy ray-curable groups, and the like.

Examples of the other acrylic resin include the same acrylic resin as the acrylic resin (b) except that the weight average molecular weight exceeds 1,100,000 or the dispersion degree is 3.0 or less.

Examples of polymers other than acrylic resins that do not have an energy ray-curable group include urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.

The weight average molecular weight (Mw) of the polymer other than the acrylic resin having no energy ray-curable group is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, from the viewpoint of improving the film-forming property of the composition (IV).

The aforementioned polymer (b0) contained in the composition (IV) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of those polymers (b0) Can choose arbitrarily.

In the composition (IV) and the protective film-forming film, the content of the polymer (b0) is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably 1 part by mass or less, and particularly preferably 0 parts by mass (i.e., the composition (IV) and the protective film-forming film do not contain the polymer (b0)). When the content of the polymer (b0) is below the upper limit, the protective film has a higher effect of suppressing the peeling of the wafer or chip.

[solvent] It is preferable that the composition (IV) further contains a solvent. The composition (IV) containing a solvent has good operability. The aforementioned solvent is not particularly limited. Examples of preferred solvents include: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1 - Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone, etc.; ethers such as tetrahydrofuran; amide such as dimethylformamide, N-methylpyrrolidone (with Compounds with amide bonds), etc. The solvent contained in the composition (IV) may be only one type, or may be two or more types. When there are two or more types, the combination and ratio of the solvents can be selected arbitrarily.

Regarding the solvent contained in the composition (IV), as a more preferable solvent in that the components contained in the composition (IV) can be mixed more uniformly, methyl ethyl ketone and the like can be cited.

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

<<Method for producing a composition for forming a protective film>> The composition for forming an energy-ray-curable protective film such as composition (IV) can be obtained by mixing the components constituting the composition. The order of addition when mixing the components is not particularly limited, and two or more components may be added simultaneously. The method for mixing the components when mixing is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade, a method of mixing by using a mixer, a method of mixing by applying ultrasonic waves, etc. The temperature and time when adding and mixing the components are not particularly limited, and may be appropriately adjusted as long as they do not deteriorate the components, and the temperature is preferably 15°C to 30°C.

Fig. 1 is a cross-sectional view schematically showing an example of a protective film forming film of the present embodiment. In addition, the following description uses a diagram, in order to facilitate understanding of the features of the present invention, for the sake of convenience, there are cases where the parts that become the main parts are enlarged to represent the situation, and the size ratios of the various constituent elements are not necessarily the same as the actual ones.

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

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

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

Regarding the protective film forming film 13 shown in FIG. 1 , when either the first release film 151 or the second release film 152 is removed, the exposed surface faces the inner surface of the wafer (not shown). Attach the surface. Then, the exposed surface produced by removing the remaining one of the first release film 151 and the second release film 152 becomes the attachment surface of the support sheet or the cutting sheet described later.

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

The protective film-forming film of this embodiment can be attached to the inner surface of the wafer without using a supporting sheet described later. In that case, a release film may be provided on the side of the protective film forming film opposite to the attachment surface facing the wafer, and the release film may be removed at an appropriate time.

On the other hand, by using the protective film-forming film of this embodiment together with a support sheet described later, a protective film-forming composite sheet capable of simultaneously forming and cutting the protective film can be constructed. Hereinafter, such a protective film forming composite sheet will be described.

◇Composite sheet for forming protective film The composite sheet for forming protective film of one embodiment of the present invention comprises: a support sheet, and a protective film forming film disposed on a surface of one side of the support sheet; the protective film forming film is the protective film forming film of one embodiment of the present invention. The composite sheet for forming protective film of this embodiment comprises the protective film forming film, and when the protective film forming film is hardened by the energy line, the degree of hardening of the protective film forming film is set to an appropriate range, thereby improving the adhesion between the protective film and the silicon wafer, and preventing the protective film from peeling off.

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

Hereinafter, each layer constituting the 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 multiple layers of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited as long as it does not impair the effect of the present invention.

The supporting sheet is preferably transparent, and can also be colored according to purpose. In this embodiment in which the protective film-forming film has energy ray curability, it is preferable that the support sheet allows energy rays to penetrate.

Examples of the supporting sheet include a supporting sheet having a substrate and an adhesive layer disposed on one side of the substrate; a supporting sheet consisting only of a substrate, etc. When the supporting sheet has an adhesive layer, in the composite sheet for forming a protective film, the adhesive layer is disposed between the substrate and the protective film forming film.

When a support sheet having a base material and an adhesive layer is used, the adhesion and releasability between the support sheet and the protective film forming film can be easily adjusted in the composite sheet for forming a protective film. When a support sheet consisting only of a base material is used, the composite sheet for forming a protective film can be manufactured at low cost.

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

FIG. 2 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film of the present embodiment. In addition, in the figures after FIG. 2, the same components as those shown in the figure that has been explained are marked with the same symbols as those in the figure that has been explained, and the detailed description of the components is omitted.

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

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

It is not limited to the case of the protective film forming composite sheet 101. In the protective film forming composite sheet of this embodiment, the release film (for example, the release film 15 shown in FIGS. 2 to 5) has an arbitrary structure. The composite sheet for forming a protective film may or may not have a release film.

The jig adhesive layer 16 is a jig for fixing the protective film forming composite sheet 101 to an annular frame or the like. The adhesive layer 16 for a jig may have a single-layer structure containing an adhesive component, for example, or may have a multiple-layer structure (including a sheet serving as a core material and layers containing an adhesive component provided on both sides of the sheet).

The composite sheet 101 for forming a protective film is used in the following manner: in a state where the release film 15 is removed, the first surface 13a of the protective film forming film 13 is attached to the inner surface of the wafer, and the first surface 16a of the jig adhesive 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 of the present embodiment. The composite sheet for forming a protective film 102 shown here is the same as the composite sheet for forming a protective film 101 shown in Fig. 2 except that the shape and size of the protective film forming film are different and the adhesive layer for the jig is laminated on the first surface of the adhesive layer instead of the first surface of the protective film forming film.

More specifically, in the protective film forming composite sheet 102, the protective film forming film 23 is laminated on a portion of the first surface 12a of the adhesive layer 12 (i.e., laminated on the central side of the adhesive layer 12 in the width direction (left-right direction in FIG. 3)). Furthermore, in the first surface 12a of the adhesive layer 12, in the area where the protective film forming film 23 is not laminated, the jig adhesive layer 16 is laminated in a non-contact manner surrounding the protective film forming film 23 from the outer side in the width direction of the protective film forming film 23. In addition, a peeling film 15 is laminated on the surface 23a of the protective film forming film 23 opposite to the adhesive layer 12 (sometimes referred to as the "first surface" in this specification) and the first surface 16a of the jig adhesive layer 16. A supporting sheet 10 is provided on the surface 23b of the protective film forming film 23 opposite to the first surface 23a (sometimes referred to as the "second surface" in this specification).

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

FIG. 5 is a cross-sectional view schematically showing yet another example of the composite sheet for forming a protective film according to this embodiment. The composite sheet 104 for protective film formation shown here is the same as the composite sheet 101 for protective film formation shown in FIG. 2 except that it is provided with the support sheet 20 instead of the support sheet 10 .

The support sheet 20 is composed only of the substrate 11. That is, the composite sheet 104 for forming a protective film is formed by laminating the substrate 11 and the protective film forming film 13 in the thickness direction of these layers. The surface (first surface) 20a on the protective film forming film 13 side of the support sheet 20 is the same as the first surface 11a of the substrate 11. The substrate 11 has adhesiveness at least on the first surface 11a of the substrate 11.

The composite sheet for forming a protective film according to this embodiment is not limited to the composite sheet for forming a protective film shown in FIGS. 2 to 5 . The composite sheet for forming a protective film may also be modified as shown in FIGS. 2 to 5 within the scope that does not impair the effect of the present invention. A part of the structure of the composite sheet for forming a protective film is changed or deleted, or other structures are added to the composite sheet for forming a protective film that has been described so far.

Next, each layer that makes up the support sheet is described in detail.

○ Substrate The aforementioned substrate is in the form of a sheet or a film, and various resins can be cited as the constituent material of the aforementioned substrate. Examples of the aforementioned resin include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylate copolymers, and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); polystyrene Ethylene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, polyesters whose entire constituent units are wholly aromatic polyesters having aromatic cyclic groups, etc.; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylate; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyether ketone, etc. In addition, as the aforementioned resin, for example, a polymer alloy such as a mixture of the aforementioned polyester and a resin other than the aforementioned polyester can also be cited. The polymer alloy of the aforementioned polyester and a resin other than the aforementioned polyester is preferably a relatively small amount of the resin other than the polyester. Furthermore, examples of the aforementioned resins include: crosslinked resins formed by crosslinking one or more of the resins mentioned above; and modified resins using ionic polymers of one or more of the resins mentioned above.

The resin constituting the substrate may be only one type or two or more types. When there are two or more types, the combination and ratio of those resins can be arbitrarily selected.

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

The thickness of the substrate is preferably 50 μm to 300 μm, more preferably 60 μm to 100 μm. When the thickness of the substrate is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to the wafer will be further improved. Here, the so-called "thickness of the substrate" means the thickness of the substrate as a whole. For example, the thickness of a substrate composed of multiple layers means the total thickness of all layers constituting the substrate.

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

The base material is preferably transparent, and can also be colored according to the purpose, and other layers can also be evaporated. In this embodiment in which the protective film-forming film has energy ray curability, it is preferable that the base material allows energy rays to penetrate.

In order to adjust the adhesion between the substrate and the layer disposed on the substrate (for example, the adhesive layer, the protective film forming film, or the aforementioned other layers), the surface of the substrate may be subjected to a roughening treatment using sandblasting, solvent treatment, etc.; an oxidation treatment such as a corona discharge treatment, an electron beam irradiation treatment, a plasma treatment, an ozone/ultraviolet irradiation treatment, a flame treatment, a chromic acid treatment, a hot air treatment, etc.; an oleophilic treatment; a hydrophilic treatment, etc. In addition, the surface of the substrate may also be subjected to a primer treatment.

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

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

○ Adhesive layer The adhesive layer is in a sheet or film form and contains an adhesive. Examples of the 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 that have adhesive properties by themselves, but also resins that exhibit adhesiveness by being used in combination with other components such as additives, and resins that exhibit adhesiveness by the presence of triggers such as heat or water. resin, etc.

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

The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm. Here, the so-called "thickness of the adhesive layer" means the thickness of the adhesive layer as a whole. For example, the thickness of an adhesive layer composed of multiple layers means the total thickness of all layers constituting the adhesive layer.

The adhesive layer is preferably transparent, and may be colored according to the purpose. In the present embodiment in which the protective film forming film has energy ray curing properties, the adhesive layer is preferably energy ray-permeable.

The adhesive layer may be either energy ray curable or non-energy ray curable. The energy ray curable adhesive layer can adjust the physical properties of the adhesive layer before and after hardening. For example, before picking up a wafer with a protective film, which will be described later, an energy ray curable adhesive layer is hardened, so that the wafer with a protective film can be picked up more easily. The adhesive layer is non-energy ray hardenable and has high light stability and excellent storage stability.

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

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

When an adhesive layer is provided on the base material, for example, it is sufficient to apply the adhesive composition on the base material and dry it if necessary. Furthermore, for example, the adhesive composition can be coated on the release film and dried if necessary, thereby forming an adhesive layer on the release film in advance, and making the exposed surface of the adhesive layer contact one side of the base material. Surface bonding, whereby an adhesive layer is laminated on a substrate. The release film in this case may be removed at any time during the manufacturing process or use of the protective film-forming composite sheet.

When the adhesive layer is energy ray curable, examples of the energy ray curable adhesive composition include a non-energy ray curable adhesive resin (I-1a) (hereinafter sometimes referred to as "Adhesive resin (I-1a)") and an adhesive composition (I-1) of an energy ray curable compound; the side chain contained in the non-energy ray curable adhesive resin (I-1a) has no problem in introducing An adhesive composition (I-2) of an energy ray-curable adhesive resin (I-2a) of saturated groups (hereinafter, sometimes referred to as "adhesive resin (I-2a)"); containing the aforementioned adhesive resin (I-2a) Adhesive composition (I-3) with an energy ray curable compound, etc.

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

[Non-energy ray curable adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably an acrylic resin.

Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate. Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a carbon number of 1 to 20. The alkyl group is preferably linear or branched. Chain.

The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from alkyl (meth)acrylate. Examples of the functional group-containing monomer include: the functional group reacts with a cross-linking agent described below to form a starting point for cross-linking; or the functional group reacts with an unsaturated group-containing compound described below. A monomer that reacts with functional groups such as isocyanate group and glycidyl group to introduce unsaturated groups into the side chains of acrylic polymers.

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

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

The aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3) and adhesive composition (I-4) (hereinafter, include the abbreviations of these adhesive compositions) In "Adhesive composition (I-1) to Adhesive composition (I-4)"), the structural unit of the acrylic resin such as the acrylic polymer may be only one type or two types. As mentioned above, in the case of two or more types, the combination and ratio of those structural units can be selected arbitrarily.

In the acrylic polymer, the amount of the constituent units derived from the monomer containing a functional group relative to the total amount of the constituent units is preferably 1 mass % to 35 mass %.

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

In the adhesive layer formed from the adhesive composition (I-1) or the adhesive composition (I-4), the content of the adhesive resin (I-1a) is relatively high relative to the total mass of the adhesive layer. Preferably, it is 5 mass% to 99 mass%, and for example, it may be any one of 25 mass% to 95 mass%, 45 mass% to 95 mass%, and 65 mass% to 95 mass%.

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

The aforementioned unsaturated group-containing compound, in addition to the aforementioned energy-beam polymerizable unsaturated group, further has the ability to react with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). A compound that is the basis of bonding. Examples of the energy ray polymerizable unsaturated group include (meth)acrylyl, vinyl (ethylidene), allyl (2-propenyl), and the like, and (meth)acryl is preferred. Jiji. Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amine group, and a carboxyl group or an epoxy group. The hydroxyl and amine groups of the knot.

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

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

In the adhesive layer formed from the adhesive composition (I-2) or the adhesive composition (I-3), the content of the adhesive resin (I-2a) is relatively high relative to the total mass of the adhesive layer. Preferably, it is 5 mass% to 99 mass%.

[Energy ray-hardening compound] As the aforementioned energy ray-hardening compound contained in the aforementioned adhesive composition (I-1) or adhesive composition (I-3), there can be cited monomers or oligomers having energy ray-polymerizable unsaturated groups and being hardenable by irradiation with energy rays.

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

The energy ray-curable compound contained in the adhesive composition (I-1) or the adhesive composition (I-3) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the energy ray-curable compounds can be arbitrarily selected.

In the adhesive layer formed by the adhesive composition (I-1) or the adhesive composition (I-3), the content of the energy ray-curable compound relative to the total mass of the adhesive layer is preferably 1 mass % to 95 mass %.

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

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

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

In the aforementioned adhesive composition (I-1) or adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 to 0.01 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a). 50 parts by mass may be, for example, any one of 1 to 40 parts by mass, 5 to 35 parts by mass, and 10 to 30 parts by mass. In the aforementioned adhesive composition (I-2) or adhesive composition (I-3), the content of the cross-linking agent is preferably 0.01 to 0.01 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). 50 parts by mass.

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

Examples of the photopolymerization initiator include the same photopolymerization initiators as those mentioned above as the photopolymerization initiator (c).

The photopolymerization initiator contained in the adhesive composition (I-1) to the adhesive composition (I-3) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of those photopolymerization initiators 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 is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray-curable compound.

[Other additives] The adhesive composition (I-1) to the adhesive composition (I-4) may also contain other additives that are not equivalent to any of the above-mentioned components within the scope that does not impair the efficacy of the present invention. As the aforementioned other additives, for example, there can be cited: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rustproofing agents, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, reaction delay agents, crosslinking promoters (catalysts) and other well-known additives. In addition, the so-called reaction retarder refers to a component that inhibits, for example, the unintended cross-linking reaction in the adhesive composition (I-1) to the adhesive composition (I-4) during storage due to the action of a catalyst mixed in the adhesive composition (I-1) to the adhesive composition (I-4). Examples of the reaction retarder include compounds that form chelate complexes by reacting with chelates directed against the catalyst, and more specifically, compounds having two or more carbonyl groups (-C(=O)-) in one molecule.

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

The content of other additives in adhesive composition (I-1) to adhesive composition (I-4) is not particularly limited and can 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. By containing a solvent, the adhesive composition (I-1) to the adhesive composition (I-4) can improve the coating suitability to the coating target surface.

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

The adhesive composition (I-1) to the adhesive composition (I-4) may contain only one type of solvent or two or more types of solvent. When there are two or more types of solvent, the combination and ratio of the solvents can be arbitrarily selected.

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

○Manufacturing method of adhesive composition Adhesive compositions such as adhesive composition (I-1) to adhesive composition (I-4) can be used to form an adhesive by formulating the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive. Obtained from each component of the composition. The adhesive composition can be produced by the same method as in the case of the protective film forming composition described above, except that the types of ingredients are different.

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

For example, when manufacturing a support sheet, when an adhesive layer is laminated on a base material, the above-mentioned adhesive composition can be coated on the base material and allowed to dry if necessary. Also, a method of coating an adhesive composition on a release film and drying it if necessary, thereby forming an adhesive layer on the release film in advance, and bonding the exposed surface of the adhesive layer to the surface of one side of the base material , this method can also laminate an adhesive layer on the substrate. At this time, the adhesive composition is preferably applied to the release-treated surface of the release film. Up to now, although the case where the adhesive layer is laminated on the base material has been taken as an example, the above method can also be applied to the case where other layers other than the adhesive layer are laminated on the base material.

On the other hand, when a protective film forming film is further formed on an adhesive layer already formed on a substrate, for example, a protective film forming film can be directly formed by coating the protective film forming composition on the adhesive layer. Layers other than the protective film forming film can also be formed by using the composition for forming the layer and by forming the layer on the adhesive layer in the same manner. In this way, when a new layer (hereinafter referred to as "the second layer") is formed on any layer (hereinafter referred to as "the first layer") already deposited on a substrate to form a continuous two-layered structure (in other words, a first layer and a second layered structure), the method of coating the composition for forming the second layer on the first layer and drying it as needed can be applied. However, it is preferred to form a continuous two-layer laminated structure by the following method: using a composition for forming the second layer, pre-forming the second layer on the release film, and attaching the exposed surface of the second layer that is opposite to the side in contact with the release film to the exposed surface of the first layer. At this time, the composition is preferably coated on the release-treated surface of the release film. After the release film forms the laminated structure, the release film can be removed as needed. Here, although the case where a protective film is laminated on an adhesive layer is taken as an example, the laminated structure to be targeted can be arbitrarily selected, such as the case where a layer (film) other than a protective film is laminated on an adhesive layer.

In this way, all layers other than the substrate constituting the composite sheet for forming a protective film can be laminated by pre-forming them on a release film and then laminating them on the surface of the target layer. Therefore, the layers using this step can be appropriately selected as needed to manufacture the composite sheet for forming a protective film.

Furthermore, the composite sheet for forming a protective film is usually stored in a state where a release film is bonded to the surface of the outermost layer (for example, the protective film-forming film) of the composite sheet for forming a protective film on the opposite side to the supporting sheet. Therefore, a composite sheet for forming a protective film with a peel film can be obtained in the following manner: a composition for forming a protective film or the like is applied on the peel film (preferably the peeling-treated surface of the peel film) to form a layer constituting the outermost layer and dried as needed, thereby forming a layer constituting the outermost layer on the peel film in advance, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the peel film by any of the above methods without removing the peel film and maintaining the bonding state unchanged.

The composite sheet for forming a protective film may be in a sheet-like form, but is preferably in a roll-like form.

◇Kit A kit of an embodiment of the present invention comprises: a first laminated body formed by sequentially laminating a first release film, a protective film forming film and a second release film, and a support sheet for supporting a workpiece to which the protective film forming film is attached and the protective film forming film; the protective film forming film is the protective film forming film of an embodiment of the present invention described above. Below, an example of the kit 1 of the present embodiment is described with reference to the drawings.

FIG. 6 is a cross-sectional view schematically showing an example of the kit 1 according to this embodiment. The kit 1 of this embodiment includes a first laminated body 5 in which a first release film 151, a protective film forming film 13, and a second release film 152 are laminated in this order, and a support for supporting the protective film forming film 13. The support sheet 10 of the film 13 is formed by attaching the workpiece and the protective film; the support sheet 10 is the support sheet of the above-mentioned embodiment of the present invention.

The protective film forming film 13 shown here has a first peeling film 151 on one side (sometimes referred to as the "first side" in this specification) 13a thereof, and has a second peeling film 152 on the other side (sometimes referred to as the "second side" in this specification) 13b which is opposite to the aforementioned first side 13a.

By using the kit 1 having the aforementioned support sheet 10 and the aforementioned protective film forming film, and utilizing the manufacturing method of a chip with a protective film described later, a chip with a protective film (having a chip and a protective film provided on the inner surface of the aforementioned chip) can be manufactured.

Such protective film-forming film 13 is suitable for storage in a roll shape, for example. That is, the first laminated body is preferably in the shape of a roll.

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

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

Regarding the protective film forming film 13 shown in Fig. 6, the exposed surface produced by removing any one of the first peeling film 151 and the second peeling film 152 becomes the attachment surface facing the inner surface of the workpiece (not shown). Then, the exposed surface produced by removing the other of the first peeling film 151 and the second peeling film 152 becomes the attachment surface of the support sheet.

In FIG. 6 , the release film is shown as an example in which the release film is provided on both sides (the first surface 13 a and the second surface 13 b ) of the protective film forming film 13 . However, the release film may be provided only on either side of the protective film forming film 13 . surface (that is, only provided on the first surface 13a or only provided on the second surface 13b).

The kit 1 of this embodiment can perform the attachment of the protective film forming film to the workpiece and the subsequent attachment of the support sheet together in an in-line process by using the protective film forming film 13 and the support sheet 10. Here, the so-called "in-line process" refers to "a process in which a device that performs one or more steps is connected to a plurality of devices (a plurality of stations), or is performed in the same device, including a plurality of steps and the transportation that connects the steps, and the workpieces are transported one by one between one step and the next step."

◇ Method for manufacturing a chip with a protective film (method for using a protective film-forming film, a composite sheet for forming a protective film, and a kit) The aforementioned protective film-forming film, the composite sheet for forming a protective film, and the kit can be used to manufacture the aforementioned chip with a protective film. That is, the method for manufacturing a chip with a protective film of the present embodiment is a method for manufacturing a chip with a protective film having a chip and a protective film disposed on the inner surface of the aforementioned chip; the method comprises the following steps: attaching the aforementioned protective film-forming film of an embodiment of the present invention to the inner surface of a wafer, thereby manufacturing a first laminated film formed by laminating the aforementioned protective film-forming film and the wafer in the thickness direction of these layers, or attaching the aforementioned composite sheet for forming a protective film of an embodiment of the present invention to the inner surface of a wafer. The protective film-forming film in the sheet is formed to produce a first laminated composite sheet in which the supporting sheet, the protective film-forming film and the wafer are sequentially laminated in the thickness direction of these layers (sometimes referred to as "attachment step" in this specification); the protective film-forming film in the first laminated film or in the first laminated composite sheet is hardened by energy beams to form the protective film, thereby producing a second laminated film in which the protective film and the wafer are laminated in the thickness direction of these layers, or producing the A step of laminating a support sheet, a protective film and a wafer in sequence in the thickness direction of these layers to form a second laminated composite sheet (sometimes referred to as a "hardening step" in this specification); in a state where a cutting sheet is provided on the protective film side of the second laminated film, the wafer in the second laminated film is divided and the protective film is cut to produce a third laminated film in which a plurality of wafers with protective films are fixed on the cutting sheet, or the wafer in the second laminated composite sheet is divided. The protective film is cut to produce a third laminated sheet in which a plurality of chips with protective films are fixed on the support sheet (sometimes referred to as "splitting step" in this specification); and a step of picking up the chips with protective films in the third laminated sheet by pulling them off from the cutting sheet or by pulling them off from the support sheet (sometimes referred to as "picking up step" in this specification).

Below, with reference to the drawings, the following two manufacturing methods are explained in sequence: a method for manufacturing a chip with a protective film in which a protective film-forming film that does not constitute a composite sheet for protective film formation (that is, the protective film-forming film in the aforementioned kit) is attached to the inner surface of a wafer (sometimes referred to as "manufacturing method 1" in this manual), and a method for manufacturing a chip with a protective film in which a protective film-forming film in a composite sheet for protective film formation is attached to the inner surface of a wafer (sometimes referred to as "manufacturing method 2" in this manual).

<<Manufacturing method 1>> FIG. 7 is a cross-sectional view schematically illustrating manufacturing method 1. Here, the manufacturing method 1 is explained by taking the case of using the protective film forming film 13 shown in FIG. 1, more specifically, the case of using the kit shown in FIG. 6 as an example. In the aforementioned attachment step of manufacturing method 1, as shown in FIG. 7(a), the protective film forming film 13 is attached to the inner surface 9b of the wafer 9, thereby manufacturing a first laminated film 601 in which the protective film forming film 13 and the wafer 9 are laminated in the thickness direction of these layers. The first surface 13a of the protective film forming film 13 is attached to the inner surface 9b of the wafer 9. The second peeling film 152 is provided on the second surface 13b of the protective film forming film 13. Although the description here is for the case where the first peeling film 151 is removed from the protective film forming film 13 shown in FIG. 1 and the first surface 13a of the protective film forming film 13 is attached to the inner surface 9b of the wafer 9, the second peeling film 152 may be removed from the protective film forming film 13 shown in FIG. 1 and the second surface 13b of the protective film forming film 13 may be attached to the inner surface 9b of the wafer 9.

The protective film forming film 13 can be attached to the wafer 9 by a known method. For example, the protective film forming film 13 may be attached to the wafer 9 while being heated.

Next, in the aforementioned hardening step of the manufacturing method 1, the protective film forming film 13 in the first laminated film 601 is hardened by energy rays to form a protective film 13', as shown in FIG7(b), thereby manufacturing a second laminated film 602 constituted by laminating the protective film 13' and the wafer 9 in the thickness direction of these layers. The symbol 13a' indicates the surface of the protective film 13' that was once the first surface 13a of the protective film forming film 13 (sometimes referred to as the "first surface" in this specification). The symbol 13b' indicates the surface of the protective film 13' that was once the second surface 13b of the protective film forming film 13 (sometimes referred to as the "second surface" in this specification).

In the aforementioned hardening step, the protective film forming film 13 of the first laminate film 601 is irradiated with energy rays from the outside through the second release film 152 (penetrating the second release film 152) to form the protective film 13'. In the aforementioned hardening step, the second release film 152 is removed from the protective film forming film 13 in the first laminate film 601 to expose the second surface 13b of the protective film forming film 13, and then the protective film forming film 13 is irradiated with energy rays to form the protective film 13'.

The energy ray irradiation conditions in the aforementioned hardening step are as described previously.

The protective film forming film 13 shown in FIG. 7(a) may be irradiated with laser through the second peeling film 152 (penetrating the second peeling film 152), or the laser marking may be performed through the second peeling film 152. The film 152 (penetrating the second release film 152) irradiates the protective film 13' shown in FIG. 7(b) with laser to perform laser marking.

Next, in the aforementioned splitting step of the manufacturing method 1, the second peeling film 152 is first removed from the protective film 13' in the second laminate film 602. Then, the surface of one side of the cutting sheet 8 (sometimes referred to as the "first surface" in this specification) 8a is attached to the second surface 13b' of the protective film 13' newly exposed thereby, as shown in FIG. 7(c). The cutting sheet 8 shown here is composed of a substrate 81 and an adhesive layer 82 disposed on a surface 81a on one side of the substrate 81, and the adhesive layer 82 in the cutting sheet 8 is attached to the protective film 13'. The surface of the adhesive layer 82 on the protective film 13' side (sometimes referred to as the "first surface" in this specification) 82a is the same as the first surface 8a of the cutting sheet 8.

The cutting blade 8 may also be a known cutting blade. For example, the base material 81 may be the same as the base material in the composite sheet for protective film formation, and the adhesive layer 82 may be the same adhesive layer as the adhesive layer in the composite sheet for protective film formation. agent layer. That is, the cutting piece 8 can be replaced by the supporting piece 10 .

Here, although the case where the dicing sheet 8 having the base material 81 and the adhesive layer 82 is used is shown, in the aforementioned dividing step, a dicing sheet other than the dicing sheet 8 may also be used, for example, only the base material 81 may be used. A cutting piece made of raw materials is used as a cutting piece.

Next, in the aforementioned dividing step, as shown in FIG7(d), the wafer 9 in the second laminate film 602 is divided and the protective film 13' is cut off with the dicing blade 8 being placed on the side of the protective film 13' of the second laminate film 602. The wafer 9 is singulated by dividing into a plurality of chips 90.

The division of the wafer 9 and the cutting of the protective film 13' may be performed by known methods. For example, the division of the wafer 9 and the cutting of the protective film 13' can be performed continuously by cutting using blade cutting, laser cutting using laser irradiation, or water cutting using spraying of water containing abrasive. . Regardless of the cutting method, the protective film 13' is cut along the periphery of the wafer 90.

In this way, the wafer 9 is divided and the protective film 13' is cut, thereby obtaining a plurality of chips 901 with protective films, which have a chip 90 and a protective film (sometimes simply referred to as a "protective film") 130' disposed on the inner surface 90b of the chip 90 after the cut. The symbol 130b' indicates a surface of the protective film 130' after the cut that was once the second surface 13b' of the protective film 13' (sometimes referred to as the "second surface" in this specification).

In the aforementioned dividing step of the manufacturing method 1, the plurality of chips 901 with protective films are fixed on the dicing sheet 8 to form the third laminate film 603 in the above manner.

Next, in the aforementioned picking-up step of the manufacturing method 1, as shown in FIG. 7(e), the chip 901 with the protective film in the third laminate film 603 is picked up by pulling it off from the dicing sheet 8. In the aforementioned picking-up step, peeling occurs between the second surface 130b' of the protective film 130' in the chip 901 with the protective film and the first surface 82a of the adhesive layer 82 in the dicing sheet 8.

Here, it is shown that the wafer 901 with the protective film is separated in the direction of arrow P using a separation means 7 such as a vacuum collet. In addition, the cross section of the separation means 7 is omitted here. The wafer 901 with the protective film can be picked up by a known method.

When the adhesive layer 82 is energy ray hardenable, it is preferable that in the aforementioned pick-up step, the adhesive layer 82 is irradiated with energy rays to harden the adhesive layer 82 to form a hardened product (not shown), Pull the wafer 901 with the protective film away from the dicing piece 8 . In this case, peeling occurs between the protective film 130' in the protective film-attached wafer 901 and the hardened material of the adhesive layer 82 in the dicing blade 8 during the aforementioned pickup step. In this case, since the cured product of the adhesive layer 82 is less likely to deform than before curing, the wafer 901 with the protective film can be picked up more easily.

In the aforementioned picking-up step, the irradiation conditions of the energy beam to the adhesive layer 82 may be the same as, for example, the irradiation conditions of the energy beam to the protective film forming film 13 in the aforementioned hardening step.

In this specification, even after the energy ray curing adhesive layer is energy ray cured, as long as the laminated structure of the substrate and the cured product of the energy ray curing adhesive layer is maintained, the laminated structure is referred to as a "cutting sheet".

On the other hand, when the adhesive layer 82 is non-energy ray-curable, the chip 901 with the protective film can be directly pulled off from the adhesive layer 82. Since the adhesive layer 82 does not need to be cured, the chip 901 with the protective film can be picked up in a simplified step. Even if the adhesive layer 82 is energy ray-curable, the chip 901 with the protective film can be picked up without curing the adhesive layer 82, and the chip 901 with the protective film can be picked up in a simplified step.

In the aforementioned picking step, all the target chips 901 with protective films are picked up.

In the manufacturing method 1, by performing the above-mentioned picking-up step, the target chip 901 with a protective film is obtained.

In conventional energy-ray curable protective film-forming films, the protective film-forming film is irradiated with energy rays through a release film. If the protective film-forming film is excessively hardened, the adhesion between the protective film and the silicon wafer will be reduced. , the protective film becomes easy to peel off, which may cause problems in subsequent manufacturing of semiconductor devices. In the manufacturing method 1, since the above-described protective film-forming film according to one embodiment of the present invention is used, when the protective film-forming film is cured by energy rays, the degree of curing of the protective film-forming film is set to an appropriate range. This improves the adhesion between the protective film and the silicon wafer and prevents the protective film from peeling off.

＜＜Manufacturing method 2＞＞ FIG. 8 is a cross-sectional view schematically explaining the manufacturing method 2. Here, the case where the protective film forming composite sheet 101 shown in FIG. 2 is used is taken as an example, and the manufacturing method 2 is demonstrated. In the aforementioned attaching step of the manufacturing method 2, as shown in FIG. 8(a) , the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the inner surface 9b of the wafer 9, thereby producing a supporting sheet. 10. The protective film forming film 13 and the wafer 9 are sequentially laminated in the thickness direction of these layers to form the first laminated composite sheet 501. In this case, the first surface 13 a of the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the inner surface 9 b of the wafer 9 in the same manner as in the manufacturing method 1.

The protective film forming film 13 in the protective film forming composite sheet 101 can be attached to the wafer 9 by a known method. For example, the protective film forming film 13 can be attached to the wafer 9 while being heated.

Next, in the aforementioned hardening step of the manufacturing method 2, the protective film-forming film 13 in the first laminated composite sheet 501 is subjected to energy ray hardening to form a protective film 13', as shown in FIG. 8(b), whereby the support is produced. The sheet 10, the protective film 13' and the wafer 9 are sequentially laminated in the thickness direction of these layers to form a second laminated composite sheet 502.

In the aforementioned hardening step, energy rays are irradiated to the protective film forming film 13 from the outside of the supporting sheet 10 side of the first laminate composite sheet 501 through the supporting sheet 10 (penetrating the supporting sheet 10), thereby forming a protective film 13'.

The aforementioned hardening step can be performed in the same manner as the hardening step in the manufacturing method 1 except that the first laminated composite sheet 501 is used instead of the first laminated film 601 .

The second laminated composite sheet 502 obtained in the aforementioned hardening step has the same structure as the laminated material of the second laminated film 602 and the cut sheet 8 in the segmentation step of the manufacturing method 1. When the cut sheet 8 is the same as the supporting sheet 10, the second laminated composite sheet 502 is the same as the aforementioned laminated material.

Next, in the aforementioned dividing step of the manufacturing method 2, as shown in Fig. 8(c) , the wafer 9 in the second laminated composite sheet 502 is divided and the protective film 13' is cut. The wafer 9 is divided into individual pieces and becomes a plurality of wafers 90 .

The aforementioned dividing step can be performed in the same manner as the dividing step in the manufacturing method 1 except that the second laminated composite sheet 502 is used instead of the laminate of the second laminated film 602 and the dicing sheet 8 . Even in the manufacturing method 2, the protective film 13' is cut along the periphery of the wafer 90 regardless of the cutting method.

In this way, the wafer 9 is divided and the protective film 13' is cut off, thereby obtaining a plurality of chips 901 with protective films having a chip 90 and a protective film 130' provided on the inner surface 90b of the chip 90 after the cut. These chips 901 with protective films obtained by the aforementioned dividing step in the manufacturing method 2 are the same as the chips 901 with protective films obtained by the dividing step in the manufacturing method 1.

The protective film forming film 13 shown in FIG. 8(a) can also be irradiated with a laser through the support sheet 10 (penetrating the support sheet 10), or laser marking can be performed via the support sheet 10 (penetrating the support sheet 10). Sheet 10) irradiates the protective film 13' shown in Figure 8(b) with laser to perform laser marking.

In the aforementioned splitting step of manufacturing method 2, the plurality of chips 901 with protective films are fixed on the support sheet 10 to form a third laminated composite sheet 503 in the above manner. The third laminated composite sheet 503 has the same structure as the third laminated film 603 obtained in the splitting step of manufacturing method 1. In the case where the cutting sheet 8 is the same as the support sheet 10, the third laminated composite sheet 503 is the same as the third laminated film 603.

Next, in the aforementioned pickup step of the manufacturing method 2, as shown in FIG. 8(d) , the wafer 901 with the protective film in the third laminated composite sheet 503 is pulled away from the support sheet 10 and picked up. In the aforementioned pickup step, peeling occurs between the second surface 130b' of the protective film 130' in the wafer 901 with the protective film and the first surface 12a of the adhesive layer 12 in the support sheet 10.

The aforementioned picking-up step can be performed in the same manner as the picking-up step in the manufacturing method 1, except that the third laminated composite sheet 503 is used instead of the third laminated film 603.

For example, when the adhesive layer 12 is energy ray hardenable, it is preferable to harden the adhesive layer 12 by irradiating energy rays to the adhesive layer 12 in the aforementioned pick-up step (illustration omitted). After that, the chip 901 with the protective film is pulled away from the support sheet 10 . In this case, peeling occurs between the protective film 130' in the wafer 901 with a protective film and the hardened material of the adhesive layer 12 in the support sheet 10 during the aforementioned pickup step. In this case, since the adhesive force between the hardened material of the adhesive layer 12 and the protective film 130' is smaller than the adhesive force between the adhesive layer 12 and the protective film 130', it is easier to pick up the wafer 901 with the protective film.

On the other hand, when the adhesive layer 12 is non-energy ray-curable, the chip 901 with the protective film can be directly pulled off from the adhesive layer 12. Since the adhesive layer 12 does not need to be cured, the chip 901 with the protective film can be picked up in a simplified step. Even if the adhesive layer 12 is energy ray-curable, the chip 901 with the protective film can be picked up without curing the adhesive layer 12, and the chip 901 with the protective film can be picked up in a simplified step.

In the manufacturing method 2, by performing the above-mentioned picking-up step, the target chip 901 with a protective film can be obtained. The chip 901 with a protective film obtained in the manufacturing method 2 is the same as the chip 901 with a protective film obtained in the manufacturing method 1.

In a conventional composite sheet for protective film formation having a protective film-forming film having energy ray curability, the protective film-forming film is irradiated with energy rays through the support sheet 10. If the protective film-forming film is excessively hardened, the protective film will be The adhesion to the silicon wafer will be reduced, and the protective film will be easily peeled off, which may cause problems in the subsequent manufacturing of semiconductor devices. In the manufacturing method 2, since the above-mentioned protective film-forming composite sheet having the protective film-forming film according to an embodiment of the present invention is used, the protective film is formed when the energy ray of the protective film-forming film is cured. The degree of hardening of the film is set to an appropriate range, thereby improving the adhesion between the protective film and the silicon wafer and preventing the protective film from peeling off.

So far, the manufacturing method 2 in which the protective film-forming composite sheet 101 shown in FIG. 2 is used has been described. However, in the manufacturing method 2, the protective film-forming composite sheet shown in FIGS. 3 to 5 may also be used. 102. The protective film forming composite sheet of this embodiment other than the protective film forming composite sheet 101 such as the protective film forming composite sheet 103 or the protective film forming composite sheet 104.

◇Manufacturing method of substrate device (how to use chips with protective film) After the wafer with a protective film is obtained by the above-mentioned manufacturing method, in addition to using the wafer with a protective film instead of the conventional wafer with a protective film, a conventional face-down substrate device can be used. The manufacturing method is the same as that used to manufacture the substrate device.

For example, the following method for manufacturing a substrate device can be cited: after a reflow step (using a reflow furnace equipped with a halogen heater to heat a circuit substrate equipped with a chip with a protective film obtained by forming a film using the above-mentioned protective film, thereby melting the protruding electrode on the chip with the protective film), the electrical connection between the protruding electrode and the connecting pad on the circuit substrate is consolidated.

The substrate device of this embodiment has excellent near-infrared shielding properties by using the above-mentioned kit having the above-mentioned protective film forming film or the above-mentioned composite sheet for protective film formation.

◇Purpose of protective film forming film The purpose of the protective film forming film of one embodiment of the present invention is to form a protective film on the surface (i.e., the inner surface) of a semiconductor wafer or a semiconductor chip that is opposite to the surface of the electric path. The aforementioned protective film forming film is the protective film forming film of one embodiment of the present invention mentioned above. The purpose of the protective film forming film of this embodiment is to set the degree of curing of the protective film forming film to an appropriate range when the protective film forming film is hardened by energy rays, thereby improving the adhesion between the protective film and the silicon wafer, and suppressing the peeling of the protective film.

The use of the protective film forming film of the present invention has the following aspects. ＜11＞ A use of the protective film forming film is to form a protective film on the surface of a semiconductor wafer or a semiconductor chip opposite to the surface of the electric path; the protective film forming film is an energy-ray-curable protective film forming film; the near-infrared transmittance of the protective film forming film at a wavelength of 1300nm is less than 10%; the curing rate ratio of the protective film forming film measured by the following curing rate ratio measurement method is greater than 1.02 and less than 100.

<Measurement method of hardening rate ratio> The aforementioned protective film-forming film was irradiated with ultraviolet rays from one side under conditions of illumination intensity 220mW/cm ² and light intensity 100mJ/cm ² , and a protective film-forming film (100) after ultraviolet irradiation was produced. . Using a Fourier transform infrared spectroscopic analysis device, FT was performed with an incident angle of 45° and the diamond ATR method on the surface (inner surface) of the protective film forming film (100) before and after ultraviolet irradiation that is opposite to the ultraviolet irradiation surface. -IR determination. After standardizing the peak intensity of the wave peak near the wave number 790 cm ^-1 to 1.5 Abs and correcting the deviation of the spectrum, the protective film forming film (100) before and after ultraviolet irradiation was placed on the inner surface of the wave peak near the wave number 810 cm ^-1 . The change in peak intensity was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film at 100 mJ/cm ² . Next, a protective film-forming film (500) after ultraviolet irradiation was produced in the same manner as above except that ultraviolet rays were irradiated under the conditions of illuminance 220 mW/cm ² and light intensity 500 mJ/cm ² . FT-IR measurement was performed on the surface (inner surface) opposite to the surface irradiated with ultraviolet rays of the protective film-forming film (500) before and after ultraviolet irradiation under the same conditions as above. After normalizing the peak intensity of the wave peak near the wave number 790 cm ^-1 to 1.5 Abs and correcting the deviation of the spectrum, the protective film forming film (500) before and after ultraviolet irradiation was placed on the inner surface of the wave peak near the wave number 810 cm ^-1 . The change in peak intensity was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film at 500 mJ/cm ² . Next, the ratio of the curing rate of the inner surface of the protective film-forming film at 500 mJ/cm ² to the curing rate of the inner surface of the protective film-forming film at 100 mJ/cm ² is calculated by the following formula (2) This was calculated as the curing rate ratio of the protective film forming film.

Curing rate = {(peak intensity before UV irradiation - peak intensity after UV irradiation) / peak intensity before UV irradiation} × 100 ・・・(1) Curing rate ratio = (curing rate of the inner surface of the protective film forming film at 500mJ/ ^cm2 ) / (curing rate of the inner surface of the protective film forming film at 100mJ/ ^cm2 ) ・・・(2)

<12> The use of the protective film forming film according to <11>, wherein an inorganic pigment is contained as a colorant. <13> The use of the protective film-forming film as described in <11> or <12> is in the production of wafers with protective films, and is used on the semiconductor wafer or the side of the semiconductor wafer that is opposite to the circuit surface. Form a protective film. <14> The use of the protective film-forming film described in <11> or <12> is in the manufacture of a face-down substrate device, on a semiconductor wafer or on the side opposite to the circuit surface. A protective film is formed on the surface. [Example]

The present invention is described in more detail below by using specific embodiments. However, the present invention is not limited to the embodiments shown below.

<Resin manufacturing raw materials> The following are the formal names of the resin manufacturing raw materials abbreviated in the present embodiment and comparative example. BA: n-butyl acrylate MA: methyl acrylate ACrMO: 4-acryloylmorpholine HEA: 2-hydroxyethyl acrylate 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate

＜Raw materials for manufacturing compositions for forming protective films＞ The raw materials used for manufacturing the protective film forming composition are shown below. [Energy ray curing component (a)] (a)-1: ε-caprolactone modified tri-(2-propenyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "A-9300-1CL", trifunctional ultraviolet curable compound ) (a)-2: Acrylic urethane ("Quick cure 8100EA70" manufactured by KJ Chemicals)

[Acrylic resin without energy-ray curing group (b)] (b)-1: Acrylic resin of copolymer of BA (33 parts by mass), MA (27 parts by mass), ACrMO (25 parts by mass) and HEA (15 parts by mass) (weight average molecular weight (700,000), glass transition temperature 2°C)

[Photopolymerization initiator (c)] (c)-1: 1-[4-(phenylthio)-2-(O-benzyl oxime)]1,2-octanedione (trade name IRGACURE (registered trademark) OXE01, manufactured by BASF Japan)

[Inorganic filler (d)] (d)-1: Spherical silica (average particle size 500nm, trade name "SC2050-MA" manufactured by Admatechs Co., Ltd.)

[Coloring agent (g)] (g)-1: Inorganic black pigment (carbon black, manufactured by Mitsubishi Carbon Black Co., Ltd., ♯20, average particle size 50nm) (g)-2: Inorganic black pigment (carbon black, manufactured by Mitsubishi Carbon Black Co., Ltd., MA600B, average particle size 20nm) (g)-3: Inorganic black pigment (carbon black, manufactured by Mitsubishi Carbon Black Co., Ltd., ♯2600, average particle size 13nm) (g)-4: Organic black pigment (carbon black, "6377 Black" manufactured by Dainichi Seika Co., Ltd.) (g)-5: Inorganic black pigment (titanium black (ingredients: titanium nitride), manufactured by Mitsubishi Materials & Electronics Co., Ltd., 13M)

<<Production of protective film forming film>> [Example 1] <Production of protective film forming composition (IV)-1> Energy ray-curable component (a)-1 (12.3 parts by mass), energy ray-curable component (a)-2 (10.0 parts by mass), acrylic resin (b)-1 (14.6 parts by mass) without energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (58.1 parts by mass) and coloring agent (g)-1 (4.0 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain energy ray-curable protective film forming composition (IV)-1 having a total concentration of all components other than the solvent of 55% by mass. In addition, the amounts of the components other than the aforementioned solvent shown here are all amounts of the target product without the solvent, and the same applies to the following protective film forming composition (IV).

＜Manufacture of protective film forming film＞ A release film (second release film, "SP-PET382150" manufactured by Lintec Co., Ltd., thickness 38 μm) made of polyethylene terephthalate and subjected to a polysiloxane treatment on one side and a release treatment was used. The protective film-forming composition (IV)-1 obtained above was coated on the release-treated surface of the release film and dried at 100° C. for 2 minutes, thereby producing an energy-beam-curable protective film-forming film with a thickness of 25 μm. .

Furthermore, a peeling-treated surface of a peeling film (a first peeling film, "SP-PET381031" manufactured by Lintec Corporation, with a thickness of 38 μm) is bonded to the exposed surface of the obtained protective film-forming film on the side not having the second peeling film, thereby obtaining a protective film-forming film with a peeling film, which comprises a protective film-forming film, a first peeling film arranged on one side of the aforementioned protective film-forming film, and a second peeling film arranged on the other side of the aforementioned protective film-forming film.

[Example 2] <Production of protective film forming composition (IV)-2> Energy ray-curable component (a)-1 (12.6 parts by mass), energy ray-curable component (a)-2 (10.2 parts by mass), acrylic resin (b)-1 (14.9 parts by mass) not having an energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (59.3 parts by mass) and coloring agent (g)-1 (2.0 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain an energy ray-curable protective film forming composition (IV)-2 having a total concentration of all components other than the solvent of 55% by mass.

＜Manufacture of protective film forming film＞ The protective film forming composition of Example 2 was produced in the same manner as in Example 1 except that protective film forming composition (IV)-2 was used instead of protective film forming composition (IV)-1. membrane.

[Example 3] <Production of protective film forming composition (IV)-3> Energy ray curable component (a)-1 (12.7 parts by mass), energy ray curable component (a)-2 (10.4 parts by mass), and acrylic resin (b)-1 (15.1) not having an energy ray curable group parts by mass), photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (59.8 parts by mass) and colorant (g)-1 (1.0 parts by mass) are melted or dispersed in Methyl ethyl ketone was stirred at 23° C., thereby obtaining an energy-beam-curable protective film-forming composition (IV)-3 in which the total concentration of all components except the solvent was 55% by mass.

＜Manufacture of protective film forming film＞ The protective film forming composition of Example 3 was produced in the same manner as in Example 1 except that protective film forming composition (IV)-3 was used instead of protective film forming composition (IV)-1. membrane.

[Example 4] <Production of protective film forming composition (IV)-4> Energy ray-curable component (a)-1 (12.6 parts by mass), energy ray-curable component (a)-2 (10.3 parts by mass), acrylic resin (b)-1 (15.0 parts by mass) without energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (59.6 parts by mass) and coloring agent (g)-1 (1.5 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain energy ray-curable protective film forming composition (IV)-4 having a total concentration of all components other than the solvent of 55% by mass.

＜Manufacture of protective film forming film＞ The protective film forming composition of Example 4 was produced in the same manner as in Example 1 except that protective film forming composition (IV)-4 was used instead of protective film forming composition (IV)-1. membrane.

[Example 5] <Production of protective film forming composition (IV)-5> Energy ray-curable component (a)-1 (12.6 parts by mass), energy ray-curable component (a)-2 (10.3 parts by mass), acrylic resin (b)-1 (15.0 parts by mass) without energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (59.4 parts by mass) and coloring agent (g)-1 (1.7 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain energy ray-curable protective film forming composition (IV)-5 having a total concentration of all components other than the solvent of 55% by mass.

<Production of protective film-forming film> The protective film-forming film of Example 5 was produced by the same method as in Example 1, except that the protective film-forming composition (IV)-5 was used instead of the protective film-forming composition (IV)-1.

[Example 6] <Production of protective film forming composition (IV)-6> Energy ray-curable component (a)-1 (12.5 parts by mass), energy ray-curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.8 parts by mass) without energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (58.6 parts by mass) and coloring agent (g)-5 (3.0 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain energy ray-curable protective film forming composition (IV)-6 having a total concentration of all components other than the solvent of 55% by mass.

＜Manufacture of protective film forming film＞ The protective film forming composition of Example 6 was produced in the same manner as in Example 1 except that protective film forming composition (IV)-6 was used instead of protective film forming composition (IV)-1. membrane.

[Example 7] <Production of protective film forming composition (IV)-7> Energy ray-curable component (a)-1 (12.6 parts by mass), energy ray-curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.9 parts by mass) not having an energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (58.7 parts by mass), colorant (g)-1 (0.5 parts by mass), colorant (g)-5 (2.2 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain energy ray-curable protective film forming composition (IV)-7 having a total concentration of all components other than the solvent of 55% by mass.

＜Manufacture of protective film forming film＞ The protective film forming composition of Example 7 was produced in the same manner as in Example 1 except that protective film forming composition (IV)-7 was used instead of protective film forming composition (IV)-1. membrane.

[Comparative Example 1] <Production of protective film forming composition (X)-1> Energy ray-curable component (a)-1 (12.9 parts by mass), energy ray-curable component (a)-2 (10.5 parts by mass), acrylic resin (b)-1 (15.3 parts by mass) not having an energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass) and inorganic filler (d)-1 (60.3 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain an energy ray-curable protective film forming composition (X)-1 having a total concentration of all components other than the solvent of 55% by mass.

＜Manufacture of protective film forming film＞ The protective film forming composition of Comparative Example 1 was produced in the same manner as in Example 1 except that protective film forming composition (X)-1 was used instead of protective film forming composition (IV)-1. membrane.

[Comparative example 2] <Production of protective film forming composition (X)-2> Energy ray curable component (a)-1 (12.6 parts by mass), energy ray curable component (a)-2 (10.3 parts by mass), and acrylic resin (b)-1 (15.0) having no energy ray curable group parts by mass), photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (59.1 parts by mass) and colorant (g)-4 (2.0 parts by mass) are melted or dispersed in Methyl ethyl ketone was stirred at 23°C to obtain an energy-beam-curable protective film-forming composition (X)-2 in which the total concentration of all components except the solvent was 55% by mass.

<Production of protective film-forming film> A protective film-forming film of Comparative Example 2 was produced by the same method as in Example 1, except that the protective film-forming composition (X)-2 was used instead of the protective film-forming composition (IV)-1.

[Comparative Example 3] <Production of protective film forming composition (X)-3> Energy ray-curable component (a)-1 (12.7 parts by mass), energy ray-curable component (a)-2 (10.7 parts by mass), acrylic resin (b)-1 (15.0 parts by mass) not having an energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (60.1 parts by mass) and coloring agent (g)-3 (0.5 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain energy ray-curable protective film forming composition (X)-3 having a total concentration of all components other than the solvent of 55% by mass.

＜Manufacture of protective film forming film＞ A protective film forming composition of Comparative Example 3 was produced in the same manner as in Example 1 except that protective film forming composition (X)-3 was used instead of protective film forming composition (IV)-1. membrane.

[Comparative Example 4] <Production of protective film forming composition (X)-4> Energy ray-curable component (a)-1 (12.8 parts by mass), energy ray-curable component (a)-2 (10.4 parts by mass), acrylic resin (b)-1 (15.2 parts by mass) not having an energy ray-curable group, photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (60.1 parts by mass) and coloring agent (g)-1 (0.5 parts by mass) were melted or dispersed in methyl ethyl ketone and stirred at 23°C to obtain energy ray-curable protective film forming composition (X)-4 having a total concentration of all components other than the solvent of 55% by mass.

<Production of protective film-forming film> A protective film-forming film of Comparative Example 4 was produced by the same method as in Example 1, except that the protective film-forming composition (X)-4 was used instead of the protective film-forming composition (IV)-1.

＜＜Evaluation of protective film forming film＞＞ ＜Measurement of transmittance of protective film forming film＞ The first peeling film and the second peeling film were peeled off, and the light transmittance of the protective film forming film was measured using an ultraviolet/visible light/near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-3600) under the following transmittance measurement conditions.

(Transmittance measurement conditions) Wavelength range: 190nm to 2000nm Scanning speed: high speed Slit width: 8.0mm Detector unit: direct light reception

<Evaluation of near-infrared shielding properties of protective film-forming films> The results of the measurement of the transmittance at a wavelength of 365nm and a wavelength of 1300nm are shown in Tables 1 to 3. Furthermore, the near-infrared shielding properties were evaluated according to the following criteria. A: The near-infrared transmittance at a wavelength of 1300nm is less than 10%, and the near-infrared shielding properties are excellent. B: The near-infrared transmittance at a wavelength of 1300nm exceeds 10%, and the near-infrared shielding properties are poor.

<Measurement of the hardening rate ratio of the protective film-forming film> A UV irradiation device (RAD-2000m/12, Lintec) was used to measure the protective film-forming film in a state in which the first release film and the second release film were laminated on the obtained above-mentioned film. company), irradiating ultraviolet rays from one surface under conditions of illumination intensity 220 mW/cm ² and light intensity 100 mJ/cm ² to produce a protective film-forming film (100) after ultraviolet irradiation. At this time, the silicon wafer is laminated on the area opposite to the incident side of the light and irradiated. Using a Fourier transform infrared/near-far infrared spectroscopic analyzer ("Spectrum 100" manufactured by PerkinElmer), a protective film is formed on the surface of the film (100) opposite to the surface irradiated with ultraviolet rays (inner surface) before and after ultraviolet irradiation. , FT-IR measurement was carried out with the incident angle of 45° and the diamond ATR method. After normalizing the peak intensity of the wave peak near the wave number 790 cm ^-1 to 1.5 Abs and correcting the deviation of the spectrum, the protective film forming film (100) before and after ultraviolet irradiation was used to determine the intensity of the wave peak near the wave number 810 cm ^-1 on the inner surface of the film (100). The change in peak intensity was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film at 100 mJ/cm ² . In addition, the crest of 790cm ^-1 is derived from (d)-1. Furthermore, the peak at 810 cm ^-1 is derived from the vinyl groups of the energy ray curable component (a)-1 and the energy ray curable component (a)-2. The greater the peak intensity, means that unreacted vinyl remains. , the protective film forming film is not sufficiently hardened. Next, a protective film-forming film (500) after ultraviolet irradiation was produced in the same manner as above except that ultraviolet rays were irradiated under the conditions of illuminance 220 mW/cm ² and light intensity 500 mJ/cm ² . FT-IR measurement was performed on the surface (inner surface) opposite to the surface irradiated with ultraviolet rays of the protective film-forming film (500) before and after ultraviolet irradiation under the same conditions as above. After standardizing the peak intensity of the wave peak near the wave number 790cm ^-1 to 1.5 Abs and correcting the deviation of the spectrum, the protective film forming film (500) before and after ultraviolet irradiation was placed on the inner surface of the wave peak near the wave number 810cm ^-1 . The change in peak intensity was calculated by the following formula (1), and this was taken as the curing rate of the inner surface of the protective film forming film at 500 mJ/cm ² .

Curing rate = {(peak intensity before UV irradiation - peak intensity after UV irradiation) / peak intensity before UV irradiation} × 100 ・・・(1)

Next, the ratio of the curing rate of the inner surface of the protective film-forming film at 500 mJ/cm ² to the curing rate of the inner surface of the protective film-forming film at 100 mJ/cm ² is calculated by the following formula (2) This was calculated as the curing rate ratio of the protective film forming film.

Hardening rate ratio = (hardening rate of the inner surface of the protective film forming film at 500mJ/cm ² )/(hardening rate of the inner surface of the protective film forming film at 100mJ/cm ² )・・・(2)

The results are shown in Table 1 to Table 3.

<Cross-cut test evaluation of protective film forming film> The second peeling film was removed from the protective film forming film with peeling film obtained above. Furthermore, a silicon wafer (diameter 200mm, thickness 350μm) with one side polished by #2000 was prepared. Using a tape laminating machine ("Adwill RAD-3600F/12 manufactured by Lintec Corporation), the protective film forming film was heated to 70°C while the exposed surface (the surface with the second peeling film) was attached to the polished surface of the aforementioned silicon wafer at 0.3MPa, thereby producing a silicon wafer with a protective film forming film in which the first peeling film, the aforementioned protective film forming film, and the aforementioned silicon wafer were sequentially laminated in the thickness direction of these layers (the aforementioned attaching step).

Next, the silicon wafer with the protective film-forming film obtained above was left to stand for 20 minutes in an environment of 23°C and 50% RH, and then the UV irradiation device ("Adwill RAD-2000M/ manufactured by Lintec Corporation") was used. 12"), irradiate ultraviolet light under the conditions of illumination intensity 220mW/cm ² and light intensity 500mJ/cm ² to produce a silicon wafer with a protective film (the aforementioned hardening step). Next, use a slitting knife on the exposed surface of the protective film in the silicon wafer with protective film obtained above, and make an incision equal to the film thickness on the protective film in the silicon wafer with protective film. The protective film is divided into 100 squares with each square being 5mm×5mm. Secondly, the first release film is removed from the 100-square silicon wafer with protective film obtained above. After that, a tape ("CELLOTAPE (registered trademark)" manufactured by NICHIBAN Co., Ltd.) was attached to the protective film side of the silicon wafer with a protective film of 100 squares in an environment of 23°C and 50% RH, and the ℃ and let it stand for 20 minutes to make the tape fully adhere to the protective film. Afterwards, the tape is peeled off, and 100 squares of silicon wafers with a protective film are used to visually confirm whether the protective film has peeled off.

At this time, the results of the cross-cut test of the protective film forming film were evaluated according to the following criteria. A: In the protective film of 100 squares, no peeling was confirmed. B: In the protective film of 100 squares, although no square was confirmed to be completely peeled, it was confirmed that the edge of 1 square was partially peeled. C: In the protective film of 100 squares, more than 1 square was confirmed to be completely peeled. The results of the cross-cut test of the protective film forming film are shown in Tables 1 to 3.

In addition, the description of “-” in the column containing components in Tables 1 to 3 means that the protective film forming film does not contain the component.

[Table 1] Example 1 2 3 4 5 protective film forming film Contains ingredients (parts by mass) Energy ray hardening component (a) (a)-1 12.3 12.6 12.7 12.6 12.6 (a)-2 10.0 10.2 10.4 10.3 10.3 Acrylic resin (b) without energy ray curable group (b)-1 14.6 14.9 15.1 15.0 15.0 Photopolymerization initiator (c) (c)-1 1.0 1.0 1.0 1.0 1.0 Inorganic filler(d) (d)-1 58.1 59.3 59.8 59.6 59.4 Colorant(g) (g)-1 4.0 2.0 1.0 1.5 1.7 (g)-2 - - - - - (g)-3 - - - - - (g)-4 - - - - - total 100 100 100 100 100 365nm penetration rate[%] 0.02 0.06 0.17 0.02 0.01 1300nm penetration rate[%] 0.04 0.3 7.5 2.1 1.4 Hardening rate of inner surface at 100mJ/cm ² [%] 1.0 15.7 68.1 24.8 22.4 Hardening rate of inner surface at 500mJ/cm ² [%] 13.1 56.0 72.9 67.4 63.1 Hardening rate ratio 13.1 3.57 1.07 2.71 2.82 Evaluation results Near infrared shielding property A A A A A Cross cutting test A A B A A

[Table 2] Embodiment 6 7 Protective film forming film Ingredients (by weight) Energy ray hardening component (a) (a)-1 12.5 12.6 (a)-2 10.1 10.1 Acrylic resin without energy ray curing group (b) (b)-1 14.8 14.9 Photopolymerization initiator (c) (c)-1 1.0 1.0 Inorganic filler (d) (d)-1 58.6 58.7 Coloring agent(g) (g)-1 - 0.5 (g)-2 - - (g)-3 - - (g)-4 - - (g)-5 3.0 2.2 Total 100 100 365nm penetration [%] 0.08 0.05 1300nm penetration [%] 1.50 1.60 Hardening rate of inner surface at 100mJ/ ^cm2 [%] 56.9 55.8 Hardening rate of the inner surface at 500mJ/ ^cm2 [%] 70.1 70.9 Hardening rate ratio 1.23 1.27 Evaluation results Near infrared shielding A A Cross cutting test A A

[table 3] Comparative example 1 2 3 4 protective film forming film Contains ingredients (parts by mass) Energy ray hardening component (a) (a)-1 12.9 12.6 12.7 12.8 (a)-2 10.5 10.3 10.7 10.4 Acrylic resin (b) without energy ray curable group (b)-1 15.3 15.0 15.0 15.2 Photopolymerization initiator (c) (c)-1 1.0 1.0 1.0 1.0 Inorganic filler(d) (d)-1 60.3 59.1 60.1 60.1 Colorant(g) (g)-1 - - - 0.5 (g)-2 - - - - (g)-3 - - 0.5 - (g)-4 - 2.0 - - total 100 100 100 100 365nm penetration rate[%] 24.0 0.20 19.2 16.0 1300nm penetration rate [%] 97.0 72.0 70.6 66.0 Hardening rate of inner surface at 100mJ/cm ² [%] 72.2 50.7 79.8 76.3 Hardening rate of inner surface at 500mJ/cm ² [%] 80.4 61.4 80.1 79.3 Hardening rate ratio 1.12 1.22 1.00 1.04 Evaluation results Near infrared shielding property B B B B Cross cutting test A A C A

As is apparent from the above results, the protective film-forming films of Examples 1 to 7 have a near-infrared transmittance of 10% or less and are excellent in near-infrared shielding. The protective film-forming films of Examples 1 to 7 have a low curing rate and can suppress peeling of the protective film after energy ray curing.

The protective film-forming film system of Comparative Example 1 has a small curing rate ratio and can suppress peeling of the protective film after energy ray curing. However, the transmittance of near-infrared rays with a wavelength of 1300 nm is 97.0%, and the shielding property of near-infrared rays is insufficient.

The protective film-forming film system of Comparative Example 2 has a small curing rate ratio and can suppress peeling of the protective film after energy ray curing. However, the transmittance of near-infrared rays with a wavelength of 1300 nm is 72.0%, and the shielding property of near-infrared rays is insufficient.

The protective film formed in Comparative Example 3 has a too low curing rate ratio, and cannot suppress the peeling of the protective film after energy ray curing. In addition, the near-infrared light transmittance of 1300nm wavelength is 70.6%, and the shielding property of near-infrared light is not sufficient.

The protective film formed by the comparative example 4 has a lower curing rate and can suppress the peeling of the protective film after energy ray curing. However, the near-infrared light transmittance of 1300nm wavelength is 66.0%, and the shielding property of near-infrared light is not sufficient. [Industrial Applicability]

The present invention can be used to manufacture various substrate devices represented by semiconductor devices.

1: Kit 10,20: Support sheet 10a,20a: Surface of one side of the support sheet (first surface) 11: Base material 11a: Surface of one side of the base material (first surface) 12: Adhesive layer 12a: Surface of one side of the adhesive layer (first surface) 13,23: Energy ray curable protective film forming film 13a,23a: Surface of one side of the protective film forming film (first surface) 13b,23b: Surface of the other side of the protective film forming film (second surface) 13': Protective film 13a': Surface of one side of the protective film (first surface) 13b': Surface of the other side of the protective film (second surface) 130': Protective film after cutting 130b': The other side of the protective film after cutting (second side) 15: Peeling film 151: First peeling film 152: Second peeling film 16: Adhesive layer for jig 16a: One side of the adhesive layer for jig (first side) 101, 102, 103, 104: Composite sheet for forming protective film 5: First laminate 501: First laminate composite sheet 502: Second laminate composite sheet 503: Third laminate composite sheet 601: First laminate film 602: Second laminate film 603: Third laminate film 7: Pulling means 8: Cutting sheet 8a: One side of cutting sheet (first side) 81: Substrate 81a: One side of substrate 82: Adhesive layer 82a: One side of adhesive layer (first side) 9: Wafer 9b: Inner surface of wafer 90: Chip 90b: Inner surface of chip 901: Chip with protective film P: Arrow

[Fig. 1] is a cross-sectional view schematically showing an example of a protective film-forming film according to an embodiment of the present invention. [Fig. 2] 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] Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 4] Fig. 4 is a cross-sectional view schematically showing yet another example of the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 5] is a cross-sectional view schematically showing yet another example of the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 6] is a cross-sectional view schematically showing an example of a kit according to an embodiment of the present invention. 7 is a cross-sectional view schematically illustrating an example of a method for manufacturing a wafer with a protective film according to an embodiment of the present invention. 8 is a cross-sectional view schematically illustrating another example of a method for manufacturing a wafer with a protective film according to an embodiment of the present invention.

13: Energy ray-hardening protective film forming film

13a: The surface of one side of the protective film forming film (first surface)

13b: The other side of the protective film forming film (second side)

151: First peeling film

152: Second peeling membrane

Claims (5)

A protective film-forming film having energy ray curability; the near-infrared ray transmittance of the aforementioned protective film-forming film having a wavelength of 1300 nm is 10% or less; the curing rate of the aforementioned protective film-forming film measured by the following method for measuring the curing rate ratio The ratio is 1.02 or more and less than 100; ＜Measurement method of hardening rate ratio＞ The aforementioned protective film forming film is irradiated with ultraviolet rays from one side under the conditions of illumination intensity 220mW/cm ² and light intensity 100mJ/cm ² to produce ultraviolet irradiation. The protective film is formed on the film (100) after the ultraviolet irradiation; using a Fourier transform infrared spectroscopic analysis device, the surface (inner surface) of the protective film forming film (100) before and after ultraviolet irradiation is opposite to the ultraviolet irradiation surface (inner surface). Angle 45°, diamond attenuated total reflection (ATR) method, Fourier transform infrared spectroscopy (FT-IR) measurement; after normalizing the peak intensity of the wave peak near the wave number 790cm ^-1 to 1.5 Abs and correcting the deviation of the spectrum, the ultraviolet Among the inner surfaces of the protective film-forming film (100) before and after irradiation, the change in the peak intensity of the wave peak near the wave number 810 cm ^-1 is calculated by the following formula (1), and this is regarded as the inner surface of the protective film-forming film The curing rate within 100mJ/cm ² ; Next, except that ultraviolet rays were irradiated under the conditions of illumination intensity 220mW/cm ² and light intensity 500mJ/cm ² , a protective film-forming film (500) after ultraviolet irradiation was produced in the same manner as above; FT-IR measurement was performed on the surface (inner surface) of the protective film-forming film (500) before and after ultraviolet irradiation that is opposite to the ultraviolet irradiation surface under the same conditions as above; the wave number was 790 cm ^-1 After normalizing the peak intensity of the nearby wave peaks to 1.5 Abs and correcting the deviation of the spectrum, the change in the peak intensity of the wave peak near the wave number of 810 cm ^-1 is determined by The following formula (1) is used to calculate the hardening rate of the inner surface of the protective film-forming film at 500mJ/cm ² ; Next, the hardening rate of the inner surface of the protective film-forming film at 500mJ/cm ² is calculated. The ratio of the curing rate of the protective film-forming film at 100 mJ/cm ² to the inner surface of the protective film-forming film is calculated by the following formula (2), and this is regarded as the curing rate ratio of the protective film-forming film; Curing rate = {(Ultraviolet rays Peak intensity before irradiation - Peak intensity after ultraviolet irradiation) / Peak intensity before ultraviolet irradiation} × 100 ・・・(1); Hardening rate ratio = (the inner surface of the protective film forming film is within 500mJ/cm ² Hardening rate)/(hardening rate of the inner surface of the protective film forming film at 100mJ/ ^cm2 )・・・(2). The protective film-forming film as recited in claim 1 contains an inorganic pigment as a coloring agent. A composite sheet for forming a protective film, which is provided with: a support sheet, and a protective film-forming film provided on one side of the support sheet; The aforementioned protective film-forming film is the protective film-forming film described in claim 1 or 2. A kit comprises: a first laminated body formed by sequentially laminating a first peeling film and a protective film forming film, and a support sheet for supporting a workpiece to which the protective film forming film is attached and the protective film forming film; The protective film forming film is the protective film forming film described in claim 1 or 2. A protective film forming film is used to form a protective film on the surface opposite to the circuit surface in a semiconductor wafer or a semiconductor chip; The aforementioned protective film forming film is a protective film forming film as described in claim 1 or 2.