TW202410168A - Protective film forming film, protective film forming composite sheet, kit, and use of protective film forming film have excellent shielding of near infrared ray and can suppress occurrence of wrinkles - Google Patents

Abstract

The invention relates to a protective film forming film 13 being energy ray-curable, which has the transmittance of near infrared at the wavelength 1300nm is below 10%. After the protective film forming film 13 is adjusted at 30 DEG C for 1 minute, the enthalpy amount ([Delta]H1) is measured while irradiating ultraviolet ray for 1 minute at conditions of an illumination 140mW / cm2 and light quantity 8120mJ/cm2 through differential scanning calorimetry (DSC). Moreover, after adjusting at 30 DEG C for 1 minute again, the enthalpy amount ([Delta]H2) is measured at the same conditions while irradiating ultraviolet ray. The enthalpy amount ([Delta]H) calculated by utilizing the formula (1) is 100J/g or more and less than 0J/g, wherein the formula (1) is [Delta]H=[Delta]H1-[Delta]H2.

Description

Protective film forming film, composite sheet for protective film forming, kit, and use of protective film forming film

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

In wafers such as semiconductor wafers or insulator wafers, there are wafers in which a circuit is first formed on one side of the surface (conductor surface), and then a protruding electrode such as a bump is formed on the surface (conductor surface). Such a wafer is divided into chips, and the protruding electrode is connected to the connection pad on the circuit substrate in a so-called face-down manner, thereby being mounted on the aforementioned circuit substrate. In such wafers or chips, in order to suppress damage such as the occurrence of cracks, a protective film is 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 may be used in the state of a protective film-forming composite sheet, or may be used without being laminated on the support sheet. After the protective film-forming film is laser-marked, in order to improve the protective performance of the protective film-forming layer, the semiconductor wafer is divided into wafers by dicing through hardening with heat or energy rays, and then picked up. Alternatively, the protective film formed by hardening the protective film forming film with heat or energy rays is laser-marked, and then the semiconductor wafer is divided into wafers by dicing and picked up. Secondly, the picked-up semiconductor wafer with a protective film is flip-chip connected to the connection pads on a circuit substrate such as a motherboard, and the circuit substrate is heated to melt the protruding electrodes on the wafer with a protective film (hereinafter, (referred to as the reflow step), the electrical connection between the protruding electrodes and the connection pads on the circuit substrate is consolidated, and the circuit substrate is constructed.

Among the protective film forming films, there is a non-curable protective film forming film that does not have curability and directly functions as a protective film in this state. In the case of using a non-curable protective film forming film, since a curing step is not required, a chip with a protective film can be manufactured at low cost by a simplified method. On the other hand, in the case of using a curable protective film forming film, since the cured product of the protective film forming film is used as the protective film, there is an advantage that the protection ability of the wafer is high. Then, the heat-curable protective film forming film that is cured by heating has a long heating time during curing, while the energy-ray-curable protective film forming film that is cured by irradiating energy rays has an advantage that the energy ray irradiation during curing can be completed in a short time. Therefore, the development of various energy-ray-curable protective film-forming films is progressing (see Patent Documents 1 to 3). [Prior Art Document] [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.

[Problem to be solved by the invention]

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, light transmittance can be reduced, and near-infrared transmittance can be reduced. However, in the known energy-ray-curable protective film forming film, if an inorganic pigment is contained to reduce near-infrared transmittance, if the protective film forming film is energy-ray-cured, wrinkles may be generated in the protective film forming film, 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 can suppress the occurrence of wrinkles during energy-ray curing, as well as to provide a composite sheet for protective film formation, 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 with energy ray curability; the near-infrared ray transmittance of the aforementioned protective film-forming film at a wavelength of 1300 nm is less than 10%; after the aforementioned protective film-forming film is tempered at 30°C for 1 minute, By differential scanning calorimetry (DSC; Differential Scanning Calorimetry), the enthalpy (ΔH1) when irradiated with ultraviolet rays for 1 minute was measured under the conditions of illuminance 140mW/cm ² and light intensity 8120mJ/cm ² , and again at 30°C. After adjusting the temperature for 1 minute, the enthalpy (ΔH2) when irradiated with ultraviolet rays for 1 minute was measured under the same conditions. The enthalpy (ΔH) calculated using the following formula (1) was -100J/g or more. to less than 0J/g. △H=△H1-△H2 ・・・(1) [2] The protective film-forming film described in [1] contains an inorganic pigment as a colorant. [3] A composite sheet for forming a protective film, comprising: a support sheet; and a protective film-forming film provided on one side of the support sheet; the protective film-forming film is as described in [1] or [2] Recorded protective film forming film. [4] A kit comprising: a first laminated body in which a first release film and a protective film-forming film are laminated in order; and a workpiece for supporting a workpiece to which the protective film-forming film is attached and the protective film-forming film The supporting sheet of the film; the aforementioned protective film-forming film is the protective film-forming film described in [1] or [2]. [5] A protective film-forming film used to form a protective film on a semiconductor wafer or a surface of a semiconductor chip opposite to the circuit surface; the aforementioned protective film-forming film is a protective film as described in [1] or [2] Membranes form membranes. [Invention effect]

According to the present invention, it is possible to provide an energy ray-curable protective film-forming film that has excellent near-infrared ray shielding properties and can suppress the occurrence of wrinkles during energy ray curing, and a protective film provided with the protective film-forming film. Use to form composite sheets, kits, and protective films to form films.

◇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 10% or less. The protective film forming film is temperature-controlled at 30°C for 1 minute, and then the enthalpy (△H1) when irradiated with ultraviolet light for 1 minute is measured by differential scanning calorimetry (DSC) under the conditions of illumination of 140mW/ ^cm2 and light quantity of 8120mJ/ ^cm2. The enthalpy (△H2) when irradiated with ultraviolet light for 1 minute is measured again under the same conditions after temperature-controlled at 30°C for 1 minute. The enthalpy (△H) obtained by the following formula (1) is -100J/g or more and less than 0J/g. △H=△H1-△H2 ・・・(1)

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 may or may not be thermosetting. When the protective film-forming film of this embodiment has both energy ray curability and thermosetting properties, the contribution of energy ray curing of the protective film-forming film to the formation of the protective film is greater than the contribution of thermal 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 that can be irradiated 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. In addition, 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 when the protective film-forming film is energy-ray cured to form a protective film are not particularly limited as long as the protective film has a degree of hardening 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 ray 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 using, for example, a commercially available ultraviolet/visible/near-infrared spectrophotometer.

The near-infrared ray transmittance of the protective film-forming film of this embodiment at a wavelength of 1300 nm is 10% or less. In order to make the near-infrared ray shielding effect more excellent, the near-infrared ray transmittance at a wavelength of 1300 nm is preferably 8% or less, and more preferably 6% or less, more preferably 4% or less. The near-infrared transmittance of the protective film forming film at a wavelength of 1300 nm may be 0.01% or more, 0.03% or more, 0.04% or more, or 0.1% or more. The near-infrared ray transmittance of the protective film-forming film of this embodiment at a wavelength of 365 nm is 10% or less. In order to make the near-infrared ray shielding effect more excellent, the near-infrared ray transmittance at a wavelength of 365 nm is preferably 5% or less, and more preferably 3% or less, more preferably 2.5% or less. The near-infrared transmittance of the protective film forming film at a wavelength of 365 nm may be 0.001% or more, 0.002% or more, or 0.003% or more.

After the protective film of the present embodiment was temperature-controlled at 30°C for 1 minute, the enthalpy (ΔH1) when irradiated with ultraviolet light for 1 minute was measured by differential scanning calorimetry (DSC) under the conditions of illuminance 140mW/ ^cm2 and light quantity 8120mJ/ ^cm2 . After the temperature was controlled at 30°C for 1 minute again, the enthalpy (ΔH2) when irradiated with ultraviolet light for 1 minute was measured under the same conditions. The enthalpy (ΔH) calculated by the following formula (1) was -100 J/g or more and less than 0 J/g. ΔH=ΔH1-ΔH2 ・・・(1)

When the enthalpy (ΔH) calculated by the formula (1) is -100 J/g or more, heat generation can be suppressed during energy ray curing of the protective film-forming film, and the generation of wrinkles in the protective film-forming film can be suppressed.

In the protective film-forming film of this embodiment, the enthalpy (ΔH) calculated using the formula (1) is -100 J/g or more. In order to more appropriately prevent the occurrence of wrinkles, the enthalpy (ΔH) calculated using the formula (1) is The enthalpy (ΔH) is preferably -90J/g or more, more preferably -80J/g or more. The protective film-forming film of this embodiment is energy ray curable, has an enthalpy (ΔH) calculated using equation (1) less than 0 J/g, and generates heat by ultraviolet irradiation.

As the protective film forming film, for example, there can be cited: an energy ray-curable component (a) and an acrylic resin (b) that does not have 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, it is not limited to the case where a protective film is formed into a film. The phrase "the plurality of layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only part of the layers may be the same." ", and "the plurality of layers are different from each other" means "at least one of the constituent materials 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, particularly preferably 5 μm to 60 μm. When the thickness of the protective film-forming film is equal to or greater than the aforementioned lower limit, a protective film with higher protective capability can be formed. By setting the thickness of the protective film-forming film below the aforementioned upper limit, the thickness of the wafer with the protective film can be prevented from becoming too thick. Here, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. For example, the thickness of the protective film-forming film having a plural-layer structure means the total thickness of all the layers constituting the protective film-forming film. "Thickness" in this specification can be determined by the method specified in JIS K 7130:1999 (ISO 4593:1993).

＜＜Protective film forming composition＞＞ The protective film forming film can be formed using an energy-ray-curable protective film forming composition containing the constituent materials of the protective film forming film (sometimes simply referred to as "protective film forming composition" in this specification). For example, the protective film forming film can be formed by applying the aforementioned protective film forming composition to the surface to be formed of the aforementioned protective film forming film and drying it as needed. The ratio of the contents of the components that do not vaporize at room temperature in the protective film forming composition is usually the same as the ratio of the contents of the aforementioned components in the protective film forming film. In this specification, the so-called "normal temperature" means a temperature that is not particularly cold or hot, that is, a normal temperature, for example, a temperature of 18°C to 28°C, etc.

The composition for forming a protective film can be coated by a known method. For example, methods using the following various coaters: air knife coater, blade coater, rod coater, gravure coater Machine, roller coater, roller knife coater, curtain coater, mold coater, knife coater, screen coater, Mayer bar coater, Light 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)> As a preferred protective film forming composition, for example, there can be cited an energy ray-curable protective film forming composition (IV) (sometimes simply referred to as "composition (IV)" in this specification) containing: the aforementioned energy ray-curable component (a), the aforementioned acrylic resin without an energy ray-curable group (b), and the aforementioned inorganic filler (d).

[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 curable group and a weight average molecular weight of 80,000 to 2,000,000) As the polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, for example, there can be cited an acrylic resin (a1-1) obtained by reacting an acrylic polymer (a11) (having a functional group capable of reacting with a group possessed by another compound) with an energy ray curable compound (a12) (having an energy ray curable group having a group reactive with the aforementioned 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 with functional groups (a11) Examples of the acrylic polymer (a11) having the functional group include an acrylic polymer copolymerized with an acrylic monomer having the functional group and an acrylic monomer not having the functional group. Examples of the acrylic polymer (a11) may be other than these. An acrylic polymer made by copolymerizing monomers other than acrylic monomers (non-acrylic monomers) in addition to monomers. In addition, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may be used as a polymerization method.

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

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

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, citric acid; anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxylalkyl esters such as 2-carboxyethyl methacrylate, and the like.

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

The acrylic monomer having a functional group constituting the acrylic polymer (a11) may be one kind or two or more kinds. When it is two or more kinds, the combination and ratio of the acrylic monomers can be arbitrarily selected.

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.

Examples of the acrylic monomer having no functional group include: (meth)acrylic acid methoxymethyl ester, (meth)acrylic acid methoxyethyl ester, (meth)acrylic acid ethoxymethyl ester , (meth)acrylic acid esters containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylate, etc.; aromatic (meth)acrylic acid aryl esters containing phenyl (meth)acrylate, etc. (meth)acrylate; non-crosslinking (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl ester, (meth)acrylic acid N,N -(Meth)acrylate with non-crosslinking tertiary amino group such as dimethylaminopropyl ester, etc.

The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one kind or two or more kinds. When it is two or more kinds, the combination and ratio of the acrylic monomers can be arbitrarily selected.

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

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

Examples of the energy ray curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and 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 aforementioned acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the aforementioned energy ray curable compound (a12) to the content of the aforementioned functional group derived from the aforementioned acrylic polymer (a11) is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and particularly preferably 50 mol% to 100 mol%. When the aforementioned content ratio is within such a range, the adhesion of the cured product of the protective film forming film becomes greater. In addition, when the aforementioned energy ray curable compound (a12) is a monofunctional compound (having one aforementioned group in one molecule), the upper limit of the aforementioned content ratio becomes 100 mol%, but when the aforementioned energy ray curable compound (a12) is a polyfunctional compound (having two or more aforementioned groups in one molecule), the upper limit of the aforementioned 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-converted value measured by gel permeation chromatography (GPC) unless otherwise stated.

The aforementioned polymer (a1) 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 (a1) Can choose arbitrarily.

(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.

As the aforementioned acrylate compound, for example, a multifunctional monomer or oligomer can be cited, and preferably a multifunctional acrylate compound having 2 or 3 or more (meth)acryloyl groups in one molecule. As the aforementioned multifunctional acrylate compound, for example, 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl] propyloxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (also known as tricyclodecane dihydroxymethyl 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)acryloyloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane and other bifunctional (meth)acrylates ((meth)acrylates having two (meth)acryloyl groups in one molecule); isocyanuric acid tris(2-(meth)acryloyloxyethyl) ester, ε-caprolactone modified isocyanuric acid tris-(2-(meth)acryloyloxyethyl) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate Multifunctional (meth)acrylates ((meth)acrylates having 3 or more (meth)acrylic groups in one molecule) such as (meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; multifunctional (meth)acrylate oligomers ((meth)acrylate oligomers having 2 or 3 or more (meth)acrylic groups in one molecule) such as multifunctional (meth)acrylic urethane oligomers, etc., 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 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 polyfunctional acrylate compound having two or more (meth)acrylyl groups per molecule, and further preferably contains a polyfunctional acrylate compound. Functional (meth)acrylic urethane oligomer is used as the energy ray curable component (a). A cured product (protective film) formed by energy ray irradiation of a protective film-forming film containing such an energy ray curable component (a) has good protective ability and flexibility, 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 except the solvent (that is, in the protective film forming film, the content ratio of the energy ray curable component (a) relative to The ratio of the total mass of 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 ratio of the energy ray curable component (a) content) is equal to or higher than the lower limit, the energy ray curability of the protective film forming film becomes Better. By setting the content ratio of the energy ray curable component (a) (that is, the content ratio of the energy ray curable component (a)) below the above upper limit, a desired protective film-forming film can be easily produced.

[Acrylic resin (b) without energy ray curing group] The aforementioned protective film-forming film preferably contains acrylic resin (b) without energy ray curing group (sometimes simply referred to as "acrylic resin (b)" in this specification).

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, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more 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 structural unit derived from 4-(meth)acrylmorpholine to the total amount of the structural units is preferably 10 mass % to 30 mass %, more preferably 13% by mass to 30% by mass, 18% by mass to 30% by mass, and 23% by mass to 30% by 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 monomer constituting the acrylic resin (b) include: (meth)acrylic acid alkyl ester, (meth)acrylic acid ester having no functional group but having a cyclic skeleton, and glycidyl group-containing (meth)acrylic acid ester. Meth)acrylate, hydroxyl-containing (meth)acrylate, substituted amine-containing (meth)acrylate, carboxyl-containing (meth)acrylate, amine-containing (meth)acrylate, etc. (Meth)acrylate; (meth)acrylamide; (meth)acrylamide derivatives such as 4-(meth)acrylylmorpholine, etc. Here, the "substituted amino group" means a group having a structure in which one or two hydrogen atoms of the amine group are substituted with groups other than hydrogen atoms. Here, the "functional group" means a group (reactive functional group) that can react with other groups, such as a glycidyl group, a hydroxyl group, a substituted amine group, a carboxyl group, and an amine group.

In this specification, the term "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid, for example, the term "(meth)acrylate" includes both "acrylate" and "methacrylate", and the term "(meth)acryl" includes both "acryl" and "methacryl".

In this specification, if a certain compound has a structure in which one or more hydrogen atoms are replaced by a group other than a hydrogen atom, the compound having such a substituted structure is referred to as a "derivative" of the above-mentioned specific compound. In this specification, the so-called "group" includes not only an atomic group formed by bonding of multiple atoms, 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 (meth)acrylate having no functional group but having a cyclic skeleton include (meth)acrylic acid esters such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate. Alkyl esters; (meth)aralkyl acrylates such as benzyl (meth)acrylate; (meth)cycloalkyl acrylates such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid dicycloalkyl esters cyclopentenoxyethyl ester, cycloalkenyloxyalkyl (meth)acrylate, etc.

Examples of the glycidyl group-containing (meth)acrylate include glycidyl (meth)acrylate. Examples of the hydroxyl-containing (meth)acrylate include the alkyl (meth)acrylate which does not have a functional group and a cyclic skeleton, and the (meth)acrylate which does not have a functional group but has a cyclic skeleton. ) One of the acrylic esters has a structure in which one or more hydrogen atoms are replaced by hydroxyl groups. Preferable examples of the hydroxyl-containing (meth)acrylate include: (meth)hydroxymethyl acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. , 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate.

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

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.

Examples of the acrylic resin (b) having a functional group include an acrylic resin obtained by polymerizing at least the monomer having a functional group. More specific examples of the acrylic resin (b) having a functional group include those selected from the group consisting of the aforementioned glycidyl group-containing (meth)acrylate, the aforementioned hydroxyl group-containing (meth)acrylate, and the aforementioned The (meth)acrylate containing a substituted amine group, the aforementioned (meth)acrylate containing a carboxyl group, the aforementioned (meth)acrylate containing an amine group, and the aforementioned non-acrylic monomer having one or more hydrogens Acrylic resin obtained by polymerizing one or more monomers from a group of monomers having a structure in which atoms are substituted by the aforementioned functional groups.

In the acrylic resin (b), the amount of the constituent units derived from the monomer having a functional group relative to the total amount of the constituent units constituting the acrylic resin (b) is preferably 1 mass % to 20 mass %, more preferably 2 mass % to 10 mass %. When the above ratio is within such a range, the degree of crosslinking in the acrylic resin (b) becomes a more preferred 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 except the solvent (that is, in the protective film forming film, the energy ray curable component The total content of the sexual component (a) and the acrylic resin (b) relative to the total mass of the protective film-forming film) is preferably 10 mass% to 60 mass%, for example, it may also be 20 mass% to 50 mass%, and Any one of 30% by mass to 45% by mass. When the aforementioned ratio is in such a range, the effect of using the energy ray curable component (a) and the acrylic resin (b) becomes higher.

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

(Photopolymerization initiator (c)) When the composition (IV) and the protective film forming film contain the photopolymerization initiator (c), the polymerization (curing) 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, benzoin 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 or two or more. When there are two or more, the combination and ratio of the photopolymerization initiators (c) can be arbitrarily selected. For example, a highly reactive photopolymerization initiator such as 2-hydroxy-2-methyl-1-phenylpropane-1-one which is liquid at room temperature can efficiently crosslink the protective film-forming film when used alone, thereby increasing the gel fraction. A low-reactive photopolymerization initiator such as 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one and 1-hydroxycyclohexyl-phenyl ketone can be used in combination with a highly-reactive photopolymerization initiator such as 2-(dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone to efficiently crosslink the protective film-forming film, thereby increasing 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 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable component (a).

(Inorganic filler (d)) When the composition (IV) and the protective film forming film contain an inorganic filler (d), the thermal expansion coefficient of the cured product of the protective film forming film (e.g., the protective film) can be more easily adjusted by adjusting the amount of the inorganic filler (d) in the composition (IV) and the protective film forming 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 is further improved. Furthermore, by using a protective film forming film containing an inorganic filler (d), the moisture absorption rate of the cured product of the protective film forming film (e.g., the protective film) can be reduced, or the heat dissipation can be improved.

Examples of the inorganic filler (d) include powders of inorganic materials such as silica, alumina, talc, calcium carbonate, titanium dioxide, titanium dioxide, silicon carbide, and boron nitride; these inorganic materials are formed into spherical shapes. beads; surface modifications of these inorganic materials; single crystal fibers of these inorganic materials; glass fibers, etc. Among these inorganic materials, the inorganic filler (d) is preferably silica or alumina. Examples of surface modified products include methoxy modification, epoxy modification, phenyl modification, and the like.

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 other than the solvent (i.e., the ratio of the content of the inorganic filler (d) to the total mass of the protective film forming film) is preferably 35% by mass to 75% by mass, and may be, for example, 45% by mass to 70% by mass, and 50% by mass to 65% by mass. By keeping the ratio within such a range, the properties of the protective film forming film are not impaired, and the effect of using the inorganic filler (d) becomes higher.

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

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 type or two or more types. In the case of two or more types, the combination and ratio of the coupling agents (e) can be Choose arbitrarily.

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, amino group, hydroxyl group, carboxyl group, isocyanate group, etc. capable of bonding with other compounds is used as the acrylic resin (b), the composition (IV) and the protective film forming film may also contain a crosslinking agent (f). The crosslinking agent (f) is a component used to crosslink the aforementioned functional groups in the acrylic resin (b) with other compounds. By crosslinking in this way, the initial adhesion and cohesion of the protective film forming film can be adjusted.

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 organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); Terpolymers, isocyanurates and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil containing low A reactant formed from a compound of molecular active hydrogen. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. In addition, the term "terminated isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

More specific examples of the organic polyisocyanate compound include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-phenylenedimethyldiisocyanate; and 1,4-phenylenediisocyanate. Methyl diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isocyanate Phorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Any one or two or more compounds of diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

Examples of the organic polyimide compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trihydroxymethylpropane-tri-β-aziridine propionate, tetrahydroxymethylmethane-tri-β-aziridine propionate, and N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylmelamine.

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 cross-linking agent (f) 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 of those cross-linking agents (f) and The ratio can be chosen arbitrarily.

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.

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

Examples of the aforementioned inorganic pigments include carbon black, titanium black, zirconium nitride, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (Indium Tin Oxide; indium tin oxide)-based pigments, ATO (Antimony Tin Oxide; antimony tin oxide)-based pigments, etc. Among these inorganic pigments, carbon black, titanium black, and zirconium nitride are particularly preferred. Carbon black is inexpensive, and titanium black is less likely to reduce the energy-ray curing property of the protective film-forming 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 caused by heat during energy-ray curing.

The content of the inorganic pigment in the composition (IV) and the protective film-forming film can be appropriately adjusted in such a manner that the transmittance of the near-infrared ray of a wavelength of 1300 nm becomes appropriate. For example, in the composition (IV), the ratio of the content of the colorant (g) to the total content of all components other than the solvent (that is, in the protective film-forming film, the ratio of the content of the colorant (g) to the total mass of the protective 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%. By making the aforementioned ratio above the aforementioned lower limit, the effect brought about by the use of the colorant (g) can be more significantly obtained. By making the aforementioned ratio below the aforementioned upper limit, the excessive use of the colorant (g) can be suppressed. Furthermore, by using multiple colorants in combination, it becomes easier to adjust the transmittance of each wavelength, which can make the cost balance better.

As the coloring agent (g), in addition to the inorganic pigment, for example, an organic pigment, an organic dye, or other known coloring agents may be contained. As the aforementioned organic pigment and organic dye, for example, amine pigments, cyanine pigments, merocyanidin pigments, crotonium pigments, squarylium pigments, azulenium pigments, polymethyl pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, peroxide pigments, and perylene pigments can be cited. Pigments, bisoxazine pigments, quinacridone pigments, isoindolinone pigments, quinolinephthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indoxyl pigments, triarylmethane pigments, anthraquinone pigments, naphthol pigments, azomethine pigments, benzimidazolone pigments, pyranthrone pigments and threonine pigments, etc.

Furthermore, by adjusting the content of the colorant (g), it is possible to adjust the laser mark visibility 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-based thermosetting resins, polyimide resins, and unsaturated polyester resins, and epoxy-based 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, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated product, o-cresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and other epoxy compounds having two or more functional groups.

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

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

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but in terms of the hardening properties 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 30,000. 10,000, especially 300 to 3,000. The epoxy equivalent of the epoxy resin (h1) is preferably 100g/eq to 1000g/eq, more preferably 150g/eq to 950g/eq.

The epoxy resin (h1) 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 of those epoxy resins (h1) and The ratio can be chosen arbitrarily.

・Thermal hardener (h2) The thermosetting agent (h2) functions as a hardening agent for the epoxy resin (h1). Examples of the thermosetting agent (h2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acidic group and the like. Preferably, a phenolic hydroxyl group, an alcoholic hydroxyl group, or an acidic group are anhydrideated. The base is preferably a phenolic hydroxyl group or an amine group.

Among the thermal curing agents (h2), examples of phenol-based curing agents having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkanes. Base phenol resin, etc. Among the thermal curing agents (h2), examples of amine-based curing agents having an amino group include dicyandiamide and the like.

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 peeling property of the protective film from the supporting sheet.

Among the thermal hardeners (h2), the number average molecular weight of resin components such as multifunctional phenol resin, novolac-type phenol resin, dicyclopentadiene-type phenol resin, aralkyl-type phenol resin, etc. is preferably 300 to 30,000. , the best value is 400 to 10,000, and the best value is 500 to 3,000. Among the thermosetting agents (h2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but 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 type, or two or more types. In the case of two or more types, the combination of those thermosetting agents (h2) and The ratio can be chosen 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 to 100 parts by mass relative to 100 parts by mass of the epoxy resin (h1). When the content of the thermosetting agent (h2) is above the lower limit, the curing of the protective film-forming film becomes easier. 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 by using the chip with the 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 the general additive (z) is used, the contents of the composition (IV) and the general additive (z) for forming a protective film are not particularly limited and can be appropriately selected according to the purpose. For example, when the general additive (z) is an ultraviolet absorber, the ratio of the content of the general additive (z) (ultraviolet absorber) to the total content of all components except the solvent in the composition (IV) (i.e., In the protective film-forming film, the content of the general additive (z) (ultraviolet absorber) relative to the total mass of the protective film-forming film) is preferably 0.1 mass % to 5 mass %. By making the aforementioned ratio above the aforementioned lower limit, the effects brought about by the use of the general additive (z) can be more significantly obtained. By keeping the ratio below the upper limit, excessive use of the general-purpose additive (z) can be suppressed.

(Other polymers (b0) without energy ray curing groups) The other polymers (b0) without energy ray curing groups impart film-forming properties to the protective film. The aforementioned polymer (b0) is not particularly limited as long as it is not equivalent to the acrylic resin (b). The aforementioned polymer (b0) may be at least partially crosslinked by a crosslinking agent or may not be crosslinked.

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 resins as those for the acrylic resin (b), except that the weight average molecular weight is higher than 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, polysiloxane 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.

The composition (IV) and the protective film-forming film may contain only one polymer (b0) or two or more polymers. When two or more polymers are contained, the combination and ratio of the polymers (b0) can be arbitrarily selected.

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 based on 100 parts by mass of the acrylic resin (b), and further preferably It is preferably 1 part by mass or less, and particularly preferably 0 part by mass (that is, the composition (IV) and the protective film-forming film do not contain the polymer (b0)). When the content of the polymer (b0) is equal to or less than the upper limit, the occurrence of wrinkles can be suppressed when the protective film-forming film is hardened by energy rays.

[Solvent] Composition (IV) preferably further contains a solvent. Composition (IV) containing a solvent has good operability. The aforementioned solvent is not particularly limited, and examples of preferred solvents include: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone, etc. The solvent contained in composition (IV) may be only one or two or more. When there are two or more solvents, the combination and ratio of those solvents can be arbitrarily selected.

As for the solvent contained in the composition (IV), for example, methyl ethyl ketone can be cited as a more preferable solvent in terms of being able to more uniformly mix the components contained in the composition (IV).

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.

＜＜Production method of protective film forming composition＞＞ A composition for forming an energy ray curable protective film such as the composition (IV) can be obtained by blending each component constituting the composition. The order in which each component is added is not particularly limited, and two or more components may be added at the same time. The method of mixing each component during preparation is not particularly limited, and can be appropriately selected from the following known methods: mixing by rotating a stirrer, stirring blade, etc.; mixing using a mixer; and mixing by applying ultrasonic waves. methods, etc. The temperature and time when adding and mixing each component are not particularly limited as long as each component is not deteriorated, and can be adjusted appropriately. 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.

The first peeling film 151 and the second peeling film 152 can be known peeling films. The first peeling film 151 and the second peeling film 152 can be the same or different from each other. For example, the peeling force required when peeling the self-protective film forming film 13 is 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, the protective film forming film of this embodiment can be used together with the support sheet described below to form a composite sheet for forming a protective film capable of forming and cutting the protective film at the same time. Hereinafter, such a composite sheet for forming a protective film will be described.

◇Composite sheet for protective film formation A protective film-forming composite sheet according to an embodiment of the present invention includes: a support sheet; and a protective film-forming film provided on one side of the support sheet; the protective film-forming film is an embodiment of the present invention described above. The protective film of the form forms the film. By including the protective film-forming film, the protective film-forming composite sheet of this embodiment can suppress the occurrence of wrinkles when the protective film-forming film is cured by energy rays.

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 piece The aforementioned supporting sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of a plurality of layers, the materials and thicknesses of the plurality of layers may be the same or different from each other. The combination of the plurality of layers is not particularly limited as long as it does not impair the effect of the present invention.

The support sheet is preferably transparent, and can also be colored according to the purpose. In the present embodiment in which the protective film forming film has energy ray curing properties, the support sheet is preferably transparent to the energy ray.

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 adhesiveness and peelability between the support sheet and the protective film-forming film can be easily adjusted in the composite sheet for protective film formation. When a support sheet composed only of a base material is used, a composite sheet for forming a protective film can be produced 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 the composite sheet for forming a protective film according to this embodiment. In addition, in the figures after FIG. 2 , the same components as those shown in the already-explained figure are assigned the same reference numerals as in the already-explained figure, and detailed descriptions of the components are 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 composite sheet 101 for forming a protective film further comprises a jig adhesive layer 16 and a release film 15 on the protective film forming film 13. In the composite sheet 101 for forming a protective film, the protective film forming film 13 is laminated on the entire surface or almost the entire surface of the first surface 12a of the adhesive layer 12, and the jig adhesive layer 16 is laminated on a part of the surface 13a of the protective film forming film 13 opposite to the adhesive layer 12 (sometimes referred to as the "first surface" in this specification), that is, the area near the peripheral portion. Furthermore, a peeling film 15 is laminated on the area of the first surface 13a of the protective film forming film 13 where the jig adhesive layer 16 is not laminated, and on the surface 16a of the jig adhesive layer 16 opposite to the protective film forming film 13 (sometimes referred to as the "first surface" in this specification). A 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 used to fix the composite sheet 101 for forming a protective film to a jig such as a ring frame. The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure (having a sheet serving as a core material and layers containing an adhesive component disposed on both sides of the sheet).

The protective film forming composite sheet 101 is used in a state where the release film 15 is removed, the inner surface of the wafer is attached to the first surface 13 a of the protective film forming film 13, and the jig adhesive layer is The first side 16a of 16 is attached to a fixture 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 .

FIG5 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film of the present embodiment. The composite sheet for forming a protective film 104 shown here is the same as the composite sheet for forming a protective film 101 shown in FIG2 except that it is configured with a support sheet 20 instead of the support sheet 10.

The support sheet 20 is composed of the base material 11 only. That is, the protective film forming composite sheet 104 is formed by laminating the base material 11 and the protective film forming film 13 in the thickness direction of these layers. The protective film forming film 13 side surface (first surface) 20 a of the support sheet 20 is the same as the first surface 11 a of the base material 11 . The base material 11 has adhesiveness on at least the first surface 11 a of the base material 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 base material is in the form of a sheet or film, and examples of the constituent material of the base material include various resins. Examples of the resin include polyethylene such as low density polyethylene (LDPE; Low Density Polyethylene), linear low density polyethylene (LLDPE; Linear Low Density Polyethylene), and high density polyethylene (HDPE; High Density Polyethylene). ; Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, Ethylene-based copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-(meth)acrylate copolymers and ethylene-norbornene copolymers; vinyl chloride-based copolymers such as polyvinyl chloride and vinyl chloride copolymers Resin (resin obtained using vinyl chloride as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polymethylene terephthalate Polyethylene phthalate, polyethylene-2,6-naphthalate, and polyesters in which all structural units are fully aromatic polyesters having aromatic ring groups; copolymerization of two or more of the above-mentioned polyesters Material; poly(meth)acrylate; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; Polyphenylene sulfide; polyurethane; polyetherketone, etc. Examples of the resin include polymer alloys such as mixtures of the polyester and resins other than the polyester. The polymer alloy of the polyester and the resin other than the polyester preferably contains a relatively small amount of the resin other than the polyester. Furthermore, examples of the resin include cross-linked resins obtained by cross-linking one or more of the above-mentioned resins; and use of one or two types of the above-mentioned resins. Modified resins such as the above ionic polymers.

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

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

By containing a specific range of components (such as resin, etc.), the base material can also have adhesiveness on at least one side.

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 aforementioned adhesive layer is in the form of a sheet or film, and contains an adhesive. Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin. .

In this specification, "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 can be composed of one layer (single layer), or it can be composed of two or more multiple layers. When it is composed of multiple layers, these multiple layers can be the same or different from each other. The combination of these multiple layers does not matter. Specially 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 entire adhesive layer. For example, the thickness of the adhesive layer having a plural-layer structure means the total thickness of all the 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 composition can be applied to a surface to be formed with an adhesive layer and dried if necessary, thereby forming an adhesive layer at a target location. The ratio of the contents of components that do not vaporize at normal temperature in the adhesive composition to each other is usually the same as the ratio of the contents of the aforementioned components to each other 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 a substrate, for example, an adhesive composition may be applied to the substrate and dried as needed. Furthermore, for example, an adhesive composition may be applied to a release film and dried as needed, thereby forming an adhesive layer on the release film in advance, and the exposed surface of the adhesive layer is bonded to the surface of one side of the substrate, thereby laminating the adhesive layer on the substrate. The release film in this case may be removed at any time during the manufacturing process or use process of the composite sheet for forming a protective film.

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 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 has a constituent unit derived from a monomer containing a functional group in addition to a constituent unit derived from an alkyl (meth)acrylate. As the monomer containing a functional group, for example, a monomer that can introduce an unsaturated group into the side chain of the acrylic polymer by reacting the functional group with the crosslinking agent described later, or by reacting the functional group with the functional group such as an isocyanate group or a glycidyl group in the unsaturated group-containing compound described later.

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 constituent units derived from other monomers in addition to constituent units derived from (meth)acrylic acid alkyl esters and constituent units derived from functional group-containing monomers. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with (meth)acrylic acid alkyl esters, etc. Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, etc.

In the aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3) and adhesive composition (I-4) (hereinafter, these adhesive compositions are referred to as "adhesive composition (I-1) to adhesive composition (I-4)"), the aforementioned acrylic polymer or the aforementioned acrylic resin may have only one type of constituent unit or may have two or more types. When there are two or more types, the combination and ratio of those constituent units can be selected arbitrarily.

In the acrylic polymer, the proportion of the structural units derived from the functional group-containing monomer relative to the total amount of the structural units is preferably 1 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 aforementioned adhesive resin (I-2a) can be obtained, for example, by reacting an unsaturated group-containing compound having an energy ray-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 kind or two or more kinds. When it is two or more kinds, the combination and ratio of those adhesive resins (I-2a) can be arbitrarily selected.

In the adhesive layer formed by the adhesive composition (I-2) or the adhesive composition (I-3), the content of the adhesive resin (I-2a) relative to the total mass of the adhesive layer is preferably 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 trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylic acid amine Formate; 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, and the like.

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

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 crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a), and may be 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 crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a).

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

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 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. parts by mass.

[Other additives] The adhesive compositions (I-1) to (I-4) may also contain other additives that are not equivalent to any of the above components within the scope that does not impair the efficacy of the present invention. Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and adhesion-imparting agents. , reaction retardants, cross-linking accelerators (catalysts) and other well-known additives. In addition, the so-called reaction delaying agent refers to, for example, an adhesive composition (I) that inhibits the action of a catalyst mixed in the adhesive composition (I-1) to the adhesive composition (I-4) during storage. -1) A component that performs an unintended cross-linking reaction in the adhesive composition (I-4). Examples of the reaction retardant include compounds that form a chelate complex by chelating the catalyst with respect to the catalyst. More specifically, examples include compounds having two or more carbonyl groups (-C(= O)-) compounds.

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

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 (carboxylic acid esters) 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.

The solvent 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, the combination and ratio of those solvents Can choose arbitrarily.

The content of the solvent in the adhesive composition (I-1) to the adhesive composition (I-4) is not particularly limited, as long as it is appropriately adjusted.

○ Method for producing adhesive composition Adhesive compositions such as adhesive composition (I-1) to adhesive composition (I-4) can be obtained by mixing the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive to form the respective components of the adhesive composition. The adhesive composition can be produced by the same method as the protective film forming composition described above, except that the types of the mixed components are different.

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

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, for example, when a protective film is laminated on an adhesive layer that has been laminated on a base material, the protective film-forming composition can be coated on the adhesive layer to directly form a protective film-forming film. The composition for forming this layer can also be used as a layer other than the protective film-forming film, and this layer can be laminated on the adhesive layer using the same method. In this way, a new layer (hereinafter referred to as the "second layer") is formed on any layer that has been laminated on the substrate (hereinafter referred to as the "first layer"), thereby forming a continuous two-layer laminate. In the case of a structure (in other words, a laminated structure of a first layer and a second layer), a method of coating the first layer with a composition for forming the second layer and drying it if necessary can be applied. However, it is preferable to form a continuous two-layer laminated structure in the following manner: using a composition for forming the second layer, forming the second layer in advance on the release film, and placing the formed second layer The side in contact with the release film is the exposed surface on the opposite side and is bonded to the exposed surface of the first layer. At this time, the composition is preferably applied to the release-treated surface of the release film. After the peeling film forms a laminated structure, it can be removed if necessary. Here, the case where a protective film-forming film is laminated on the adhesive layer is given as an example. However, for example, when a layer (film) other than the protective film-forming film is laminated on the adhesive layer, the subject laminate structure is The system can be selected arbitrarily.

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.

In addition, the protective film-forming composite sheet is usually stored in a state where a release film is bonded to the surface of the outermost layer (eg, protective film-forming film) of the protective film-forming composite sheet on the opposite side to the support sheet. Therefore, a protective film-forming composite sheet with a release film can be obtained by coating a protective film-forming composition or the like on the release film (preferably, the release-treated surface of the release film). The composition constituting the layer constituting the surface layer is formed and dried if necessary, thereby forming the layer constituting the surface layer on the release film in advance, and using any of the above methods to expose the side opposite to the side in contact with the release film. Laminate the remaining layers on the surface without removing the peel-off film and keep the bonded state intact.

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

◇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.

FIG6 is a cross-sectional view schematically showing an example of a kit 1 of the present embodiment. The kit 1 of the present embodiment comprises: a first laminate 5 formed by sequentially laminating a first release film 151, a protective film forming film 13 and a second release film 152, and a support sheet 10 for supporting a workpiece to which the protective film forming film 13 is attached and the protective film forming film 13; the protective film forming film 13 is the protective film forming film of the embodiment of the present invention described above.

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 release film 151 and the second release 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 uses the protective film-forming film 13 and the support sheet 10 together, so that the attachment of the protective film-forming film to the workpiece and the subsequent attachment of the support sheet can be performed simultaneously in an in-line process. Here, the so-called "online program" refers to "a program that connects a device that performs one or more steps to a plurality of devices (plural devices), or a program that is performed in the same device, including multiple steps and This is a procedure that links the steps to the transportation of the steps, and transports the workpieces piece by piece 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, 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 can 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 subjected to energy ray hardening to form the protective film 13', as shown in FIG. 7(b), whereby the protective film is produced. 13' and wafer 9 are laminated in the thickness direction of these layers to form a second laminated film 602. Symbol 13a' indicates the surface of the protective film 13' that was the first surface 13a of the protective film forming film 13 (sometimes referred to as the "first surface" in this specification). Symbol 13b' indicates the surface of the protective film 13' that was the second surface 13b of the protective film forming film 13 (sometimes referred to as the "second surface" in this specification).

In the aforementioned curing step, the protective film forming film 13 is irradiated with energy rays from the outside of the protective film forming film 13 side of the first laminated film 601 via the second release film 152 (penetrating the second release film 152 ). A protective film 13' is formed. In the aforementioned curing step, the second peeling film 152 may be removed from the protective film-forming film 13 in the first laminated film 601 to expose the second surface 13b of the protective film-forming film 13, and then the protective film-forming film 13 may be irradiated. Energy lines, thereby forming a protective film 13'.

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

Laser marking can also be performed by irradiating the protective film forming film 13 shown in Figure 7(a) with a laser through the second peeling film 152 (penetrating the second peeling film 152), or laser marking can also be performed by irradiating the protective film 13' shown in Figure 7(b) with a laser through the second peeling film 152 (penetrating the second peeling film 152).

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 sheet 8 may be a known cutting sheet. For example, the substrate 81 may be the same substrate as the substrate in the composite sheet for forming the protective film, and the adhesive layer 82 may be the same adhesive layer as the adhesive layer in the composite sheet for forming the protective film. That is, the cutting sheet 8 may be replaced by the supporting sheet 10.

Although the case of using the cutting sheet 8 having the base material 81 and the adhesive layer 82 is described here, in the aforementioned dividing step, a cutting sheet other than the cutting sheet 8, for example, a cutting sheet consisting only of the base material, may be used as the cutting sheet.

Next, in the aforementioned dividing step, as shown in FIG. 7(d) , with the dicing blade 8 disposed on the protective film 13' side of the second laminated film 602, the wafer 9 in the second laminated film 602 is divided and Cut off the protective film 13'. The wafer 9 is divided into individual pieces and becomes a plurality of wafers 90 .

The wafer 9 can be divided and the protective film 13' can be cut by a known method. For example, the wafer 9 can be divided and the protective film 13' can be cut continuously by blade cutting, laser cutting using laser irradiation, or water cutting using spraying of water containing an abrasive. The protective film 13' is cut along the periphery of the chip 90 regardless of the cutting method.

In this manner, the wafer 9 is divided and the protective film 13' is cut, thereby obtaining a cut protective film having the wafer 90 and being disposed on the inner surface 90b of the wafer 90 (hereinafter, sometimes simply referred to as "protective film"). A plurality of chips 901 with protective films (film) 130'. Symbol 130b' indicates the side of the cut protective film 130' that was once the second side 13b' of the protective film 13' (sometimes referred to as the "second side" in this specification).

In the aforementioned dividing step of the manufacturing method 1, in the above manner, the third laminated film 603 composed of the plurality of protective film-attached wafers 901 fixed on the dicing sheet 8 is produced.

Next, in the aforementioned pickup step of the manufacturing method 1, as shown in FIG. 7(e) , the wafer 901 with the protective film in the third laminated film 603 is pulled away from the dicing sheet 8 to be 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 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 pickup step, after 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 foregoing pickup step, the energy ray irradiation conditions for the adhesive layer 82 may also be the same as, for example, the energy ray irradiation conditions for the protective film forming film 13 in the foregoing 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 pickup step, the pickup of the protective film-attached wafers 901 is performed on all the target wafers 901 with the protective film.

In the manufacturing method 1, by proceeding to the aforementioned pickup step, the target wafer 901 with a protective film is obtained.

In conventional energy-ray curable protective film-forming films, by irradiating the protective film-forming film with energy rays through a release film, wrinkles may occur in the protective film-forming film at the outer periphery of the wafer, making it impossible to bond with the dicing wafer. Problems with sticking neatly may occur. In the manufacturing method 1, since the above-mentioned protective film-forming film according to one embodiment of the present invention is used, the occurrence of wrinkles can be suppressed when the protective film-forming film is hardened by energy rays.

＜＜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 hardened by energy lines to form a protective film 13', as shown in FIG8(b), thereby manufacturing a second laminated composite sheet 502 in which the support sheet 10, the protective film 13' and the wafer 9 are sequentially laminated in the thickness direction of these layers.

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 curing step can be performed in the same manner as the curing 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 laminate of the second laminated film 602 and the cutting sheet 8 in the dividing step of the manufacturing method 1. When the cutting sheet 8 is the same as the support sheet 10, the second laminated composite sheet 502 is the same as the aforementioned laminated product.

Next, in the aforementioned dividing step of the manufacturing method 2, as shown in FIG8(c), the wafer 9 in the second laminated composite sheet 502 is divided and the protective film 13' is cut off. The wafer 9 is singulated by dividing into a plurality of chips 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 to replace the laminated material of the second laminated film 602 and the cutting sheet 8. Even in the manufacturing method 2, the protective film 13' is cut along the periphery of the chip 90 regardless of the cutting method.

In this way, the wafer 9 is divided and the protective film 13' is cut, thereby obtaining a plurality of protective film-attached wafers 901 including the wafer 90 and the cut protective film 130' provided on the inner surface 90b of the wafer 90. . These protective film-attached wafers 901 obtained in the aforementioned dividing step in the manufacturing method 2 are the same as the protective film-attached wafers 901 obtained in the dividing step in the manufacturing method 1.

Laser marking can also be performed by irradiating the protective film forming film 13 shown in Figure 8(a) with a laser through the support sheet 10 (penetrating the support sheet 10), or laser marking can be performed by irradiating the protective film 13' shown in Figure 8(b) with a laser through the support sheet 10 (penetrating the support sheet 10).

In the aforementioned dividing step of the manufacturing method 2, in the above manner, the third laminated composite sheet 503 composed of the plurality of protective film-attached wafers 901 fixed on the support sheet 10 is produced. The third laminated composite sheet 503 has the same structure as the third laminated film 603 obtained in the dividing step of the manufacturing method 1. When 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 pick-up step of the manufacturing method 2, as shown in FIG8(d), the chip 901 with a protective film in the third laminated composite sheet 503 is picked up by pulling it off from the support sheet 10. In the aforementioned pick-up step, peeling occurs between the second surface 130b' of the protective film 130' in the chip 901 with a 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-curable, it is preferred that in the aforementioned pick-up step, after the adhesive layer 12 is hardened by irradiating the adhesive layer 12 with energy rays to form a hardened product (not shown), the chip 901 with a protective film is pulled away from the support sheet 10. In this case, in the aforementioned pick-up step, peeling occurs between the protective film 130' in the chip 901 with a protective film and the hardened product of the adhesive layer 12 in the support sheet 10. In this case, since the hardened product of the adhesive layer 12 becomes less deformable than before hardening, the chip 901 with a protective film can be picked up more easily.

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 protective film forming composite sheet having an energy ray curable protective film forming film, by irradiating the protective film forming film with energy rays through the support sheet 10, the protective film forming film is formed on the outer periphery of the wafer. Wrinkles occur, and there is a risk of adsorption errors when being adsorbed to the porous table of the cutting device. 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, wrinkles can be suppressed when the protective film-forming film is cured by energy rays. can suppress adsorption errors.

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, there is a method of manufacturing a substrate device in which a circuit board mounted on a wafer with a protective film obtained by using the protective film-forming film is heated through a reflow step (using a reflow furnace equipped with a halogen heater). , thereby melting the protruding electrodes on the chip with the protective film) and consolidating the electrical connection between the protruding electrodes and the connection pads on the circuit substrate.

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

◇ Use of protective film forming film The use 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 opposite to the circuit surface, and the aforementioned protective film forming film is the protective film forming film of one embodiment of the present invention mentioned above. The use of the protective film forming film of this embodiment is that, by having the aforementioned protective film forming film, when the protective film forming film is hardened by energy rays, heat generation can be suppressed, and wrinkles of the protective film forming film can be suppressed.

The protective film-forming film of the present invention can be used in the following aspects. <11> The use of a protective film-forming film, which is used to form a protective film on a semiconductor wafer or a surface of a semiconductor wafer that is opposite to the circuit surface; the aforementioned protective film-forming film is an energy ray-curable protective film-forming film; The near-infrared transmittance of the aforementioned protective film-forming film at a wavelength of 1300 nm is less than 10%; after adjusting the temperature of the aforementioned protective film-forming film at 30°C for 1 minute, the differential scanning calorimetry (DSC) is used to measure the temperature of the protective film-forming film with an illumination of 140 mW/ cm ² and light intensity of 8120 mJ/cm ² , measure the enthalpy (ΔH1) when irradiated with ultraviolet rays for 1 minute, and again adjust the temperature at 30°C for 1 minute, and then measure the enthalpy when irradiated with ultraviolet rays for 1 minute under the same conditions. In the case of enthalpy (ΔH2), the enthalpy (ΔH) calculated using the following formula (1) is -100 J/g or more and less than 0 J/g. △H=△H1-△H2 ・・・(1) ＜12＞ The use of protective film forming film as described in ＜11＞, which contains inorganic pigments as colorants. <13> The use of the protective film-forming film described in <11> or <12> is in the production of wafers with protective films, and is used to form a protective film on a semiconductor wafer or on 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.

＜Raw materials for manufacturing resin＞ The official names of the resin manufacturing raw materials, which are abbreviated in the present Examples and Comparative Examples, are shown below. BA: n-butyl acrylate MA: Methyl acrylate ACrMO: 4-Acrylylmorpholine 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 diameter 500 nm, 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., ♯20B, average particle size 50nm) (g)-2: Inorganic black pigment (carbon black, manufactured by Mitsubishi Carbon Black Co., Ltd., MA600B, average particle size 20 nm) (g)-3: Inorganic black pigment (carbon black, manufactured by Mitsubishi Carbon Black Co., Ltd., ♯2600, average particle size 13 nm) (g)-4: Organic black pigment (carbon black, "6377 Black" manufactured by Dainichi Seika Industrial Co., Ltd.)

<<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 process of laminating a peeling film (first peeling film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) to the exposed surface of the obtained protective film-forming film on the side not provided with the second peeling film surface, thereby obtaining a peel-off film including a protective film-forming film, a first release film provided on one side of the protective film-forming film, and a second release film provided on the other side of the protective film-forming film. The protective film of the film forms the film.

[Example 2] <Production of protective film forming composition (IV)-2> Energy ray-curable component (a)-1 (12.4 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 (58.7 parts by mass) and coloring agent (g)-1 (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)-2 having a total concentration of 55% by mass of all components other than the solvent.

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

[Example 3] <Production of protective film forming composition (IV)-3> The energy ray curable component (a)-1 (12.6 parts by mass), the energy ray curable component (a)-2 (10.2 parts by mass), and the acrylic resin (b)-1 (14.9) having no energy ray curable group were used. parts by mass), photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (59.3 parts by mass) and colorant (g)-1 (2.0 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> The same protective film forming composition (IV)-2 as in Example 2 was used except that colorant (g)-2 (3.0 parts by mass) was used instead of colorant (g)-1 (3.0 parts by mass). Composition (IV)-4 for forming a protective film was produced in the same manner as in the above case.

＜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> The same protective film forming composition (IV)-2 as in Example 2 was used except that colorant (g)-3 (3.0 parts by mass) was used instead of colorant (g)-1 (3.0 parts by mass). The protective film forming composition (IV)-5 was produced in the same manner as in the above case.

＜Manufacture of protective film forming film＞ The protective film forming composition of Example 5 was produced in the same manner as in Example 1 except that protective film forming composition (IV)-5 was used instead of protective film forming composition (IV)-1. membrane.

[Example 6] <Production of protective film forming composition (IV)-6> A protective film forming composition (IV)-6 was produced by the same method as in Example 3, except that colorant (g)-2 (2.0 parts by mass) was used instead of colorant (g)-1 (2.0 parts 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 (12.7 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)-7 in which the total concentration of all components except the solvent was 55% by mass.

<Production of protective film-forming film> The protective film-forming film of Example 7 was produced by the same method as in Example 1, except that the protective film-forming composition (IV)-7 was used instead of the protective film-forming composition (IV)-1.

[Example 8] <Production of protective film forming composition (IV)-8> 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)-8 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 8 was produced by the same method as Example 1, except that the protective film-forming composition (IV)-8 was used instead of the protective film-forming composition (IV)-1.

[Example 9] <Production of protective film forming composition (IV)-9> 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)-9 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 9 was produced by the same method as in Example 1, except that the protective film-forming composition (IV)-9 was used instead of the protective film-forming composition (IV)-1.

[Comparative example 1] <Production of protective film forming composition (X)-1> The energy ray curable component (a)-1 (12.2 parts by mass), the energy ray curable component (a)-2 (10.0 parts by mass), and the acrylic resin (b)-1 (14.4) having no energy ray curable group parts by mass), photopolymerization initiator (c)-1 (1.0 parts by mass), inorganic filler (d)-1 (57.4 parts by mass) and colorant (g)-1 (5.0 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 (X)-1 in which the total concentration of all components except the solvent was 55% by mass. In addition, the compounding amounts of the components other than the above-mentioned solvent shown here are all the compounding amounts of the target substance which does not contain a solvent, and the same applies to the following protective film forming composition (X).

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

[Comparative example 2] <Production of protective film forming composition (X)-2> Energy ray curable component (a)-1 (12.9 parts by mass), energy ray curable component (a)-2 (10.5 parts by mass), and acrylic resin (b)-1 (15.3) not having an energy ray curable group parts by mass), photopolymerization initiator (c)-1 (1.0 parts by mass) and inorganic filler (d)-1 (60.3 parts by mass) are melted or dispersed in methyl ethyl ketone, and stirred at 23°C. Thus, an energy-beam-curable protective film-forming composition (X)-2 was obtained 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 Comparative Example 2 was produced in the same manner as in Example 1 except that protective film forming composition (X)-2 was used instead of protective film forming composition (IV)-1. membrane.

[Comparative example 3] <Production of protective film forming composition (X)-3> 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 ray curable protective film forming composition (X)-3 in which the total concentration of all components except the solvent was 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.

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

(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 measurement results of the transmittance at a wavelength of 365 nm and a wavelength of 1300 nm are shown in Tables 1 to 3. In addition, near-infrared ray shielding properties were evaluated based on the following criteria. A: The near-infrared ray transmittance at wavelength 1300nm is less than 10%, and the near-infrared ray shielding property is excellent. B: The near-infrared ray transmittance of wavelength 1300nm exceeds 10%, and the near-infrared ray shielding property is poor.

<Measurement of enthalpy (ΔH) of protective film formation> Using a differential scanning calorimetry device (DSC8500 manufactured by PerkinElmer Japan Co., Ltd.), 0.4 mg to 0.7 mg of samples were collected from each protective film forming film, and the enthalpy amount (ΔH1) and enthalpy were measured in the following manner. Amount (△H2). Temperature adjustment at 30°C for 1 minute → UV (ultraviolet; ultraviolet) irradiation for 1 minute (measurement of enthalpy (△H1)) → Temperature adjustment at 30°C for 1 minute → UV irradiation for 1 minute (measurement of enthalpy (△H2))

UV light source: high-pressure mercury lamp Illumination: 140mW/cm ² Illumination intensity (irradiation time: 1 minute): 8120mJ/cm ² Filter: None (full wavelength)

The results of enthalpy (△H) obtained by the following formula (1) are shown in Tables 1 to 3. Furthermore, for reference, the mass of the protective film forming film used in the measurement is shown in Tables 1 to 3. △H=△H1-△H2　・・・(1)

[Manufacturing of a support sheet with a peeling film] 100 parts by mass (solid) of a polymer component and 40 parts by mass (solid) of a trifunctional xylylene diisocyanate crosslinking agent ("TAKENATE (registered trademark) D110N" manufactured by MITSUI TAKEDA CHEMICALS) were dissolved or dispersed in methyl ethyl ketone, and the solid concentration was adjusted to 25% by mass to obtain an adhesive composition. In addition, the above-mentioned polymer component is an acrylic copolymer having a weight average molecular weight of 400,000 and a glass transition temperature of -31°C obtained by copolymerizing 60 parts by mass of 2-ethylhexyl acrylate (2EHA), 30 parts by mass of methyl methacrylate (MMA), and 10 parts by mass of 2-hydroxyethyl acrylate (HEA).

The peeling film (SP-PET382150 manufactured by Lintec, 38 μm thick) was coated with the aforementioned adhesive composition using a knife coater and dried at 110°C for 2 minutes to form an adhesive layer (5 μm thick after drying). A polypropylene film (80 μm thick, manufactured by Gunze, 0.1 μm roughness on the shiny side and 0.3 μm roughness on the matte side) as a substrate was bonded to the exposed surface (the surface opposite to the side with the peeling film) to obtain a peeling film-attached support sheet consisting of substrate/adhesive layer/peeling film.

[Production of a composite sheet for forming a protective film] The release film is removed from the support sheet with the release film obtained above. Furthermore, the first release film is removed from the protective film forming film obtained above. Then, by laminating the exposed surface of the adhesive layer produced by removing the release film above and the exposed surface of the protective film forming film produced by removing the first release film above, a composite sheet for forming a protective film is produced in which a substrate, an adhesive layer, a protective film forming film and a second release film are sequentially layered in the thickness direction of these layers.

<Evaluation of suppression of wrinkle occurrence in protective film-forming film> The second release film was removed from the obtained composite sheet for protective film formation. Mount the 6-inch wafer and the ring-shaped frame on the composite sheet for forming a protective film with the adhesive layer exposed. After leaving it for 20 minutes, perform UV irradiation with illumination: 220mW/cm ² and light intensity: 500mJ/cm ² . Secondly, it is adsorbed to the porous table of the cutting device (manufactured by DISCO, DFD6362).

At this time, the suppression of wrinkles was evaluated based on the following criteria. A: The composite sheet for forming a protective film around a 6-inch wafer was not wrinkled and could be normally adsorbed to the porous workbench of the cutting device. B: The composite sheet for forming a protective film around a 6-inch wafer was wrinkled and could not be adsorbed to the porous workbench of the cutting device. The results of the evaluation of the suppression of wrinkles in the protective film forming film are shown in Tables 1 to 3.

In addition, the description of "-" in the column of the contained component in Tables 1 to 3 means that the protective film-forming film does not contain the component.

[Table 1] Example 1 2 3 4 protective film forming film Contains ingredients (parts by mass) Energy ray hardening component (a) (a)-1 12.3 12.4 12.6 12.4 (a)-2 10.0 10.1 10.2 10.1 Acrylic resin (b) without energy ray curable group (b)-1 14.6 14.8 14.9 14.8 Photopolymerization initiator (c) (c)-1 1.0 1.0 1.0 1.0 Inorganic filler(d) (d)-1 58.1 58.7 59.3 58.7 Colorant(g) (g)-1 4.0 3.0 2.0 - (g)-2 - - - 3.0 (g)-3 - - - - (g)-4 - - - - total 100 100 100 100 365nm penetration rate[%] 0.02 0.05 0.06 0.004 1300nm penetration rate[%] 0.04 0.1 0.3 1.4 Enthalpy △H [J/g] (mass measured by UV-DSC [mg]) -95.8(0.54) -73.1(0.51) -47.7(0.55) -72.4(0.55) Evaluation results Near infrared shielding property A A A A Inhibition of wrinkle occurrence A A A A

[Table 2] Embodiment 5 6 7 8 Protective film forming film Ingredients (by weight) Energy ray hardening component (a) (a)-1 12.4 12.6 12.7 12.6 (a)-2 10.1 10.2 10.4 10.3 Acrylic resin without energy ray curing group (b) (b)-1 14.8 14.9 15.1 15.0 Photopolymerization initiator (c) (c)-1 1.0 1.0 1.0 1.0 Inorganic filler (d) (d)-1 58.7 59.3 59.8 59.6 Coloring agent(g) (g)-1 - - 1.0 1.5 (g)-2 - 2.0 - - (g)-3 3.0 - - - (g)-4 - - - - Total 100 100 100 100 365nm penetration [%] 0.09 0.2 0.17 0.02 1300nm penetration [%] 3.3 3.4 7.5 2.1 Enthalpy △H[J/g](UV-DSC measured mass[mg]) -84.7(0.57) -47.3(0.53) -27.6(0.55) -35.8(0.6) Evaluation results Near infrared shielding A A A A Inhibition of wrinkles A A A A

[table 3] Example Comparative example 9 1 2 3 protective film forming film Contains ingredients (parts by mass) Energy ray hardening component (a) (a)-1 12.6 12.2 12.9 12.6 (a)-2 10.3 10.0 10.5 10.3 Acrylic resin (b) without energy ray curable group (b)-1 15.0 14.4 15.3 15.0 Photopolymerization initiator (c) (c)-1 1.0 1.0 1.0 1.0 Inorganic filler(d) (d)-1 59.4 57.4 60.3 59.1 Colorant(g) (g)-1 1.7 5.0 - - (g)-2 - - - - (g)-3 - - - - (g)-4 - - - 2 total 100 100 100 100 365nm penetration rate [%] 0.01 0.01 24.0 0.20 1300nm penetration rate [%] 1.4 0.02 97.0 72.0 Enthalpy △H [J/g] (mass measured by UV-DSC [mg]) -42.0(0.61) -109.2(0.57) -22.6(0.52) -34.0(0.68) Evaluation results Near infrared shielding property A A B B Inhibition of wrinkle occurrence A B A A

As is apparent from the above results, the protective film-forming films of Examples 1 to 9 have a near-infrared transmittance of 10% or less, and have excellent near-infrared shielding properties. The protective film-forming films of Examples 1 to 9 absorb and release heat when irradiated with ultraviolet rays. However, the enthalpy (ΔH) is from -100 J/g to less than 0 J/g, and wrinkles do not occur during energy ray curing, and can be normally adsorbed on the porous workbench of the cutting device.

The protective film formed by the comparative example 1 has a near-infrared transmittance of less than 10% at a wavelength of 1300nm, and has excellent near-infrared shielding properties. However, if irradiated with ultraviolet rays, the enthalpy (△H) is -109.2/g, and excessive heat is released, wrinkles occur, and it cannot be adsorbed on the porous worktable of the cutting device.

The film formation enthalpy (ΔH) of the protective film in Comparative Examples 2 to 3 was -100 J/g or more and less than 0 J/g, no wrinkles occurred during energy ray hardening, and the film could be adsorbed to the cutting device normally. Porous work surface. However, the transmittance of near-infrared rays with a wavelength of 1300 nm is 72% to 97%, and the shielding property of near-infrared rays is poor. [Industrial Availability]

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 of an embodiment of the present invention. [FIG. 2] is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film of an embodiment of the present invention. [FIG. 3] is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film of an embodiment of the present invention. [FIG. 4] is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film of an embodiment of the present invention. [FIG. 5] is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film of an embodiment of the present invention. [FIG. 6] is a cross-sectional view schematically showing an example of a kit of an embodiment of the present invention. [FIG. 7] is a cross-sectional view schematically illustrating an example of a method for manufacturing a chip with a protective film of an embodiment of the present invention. [Figure 8] is a cross-sectional view schematically illustrating another example of a method for manufacturing a chip with a protective film in 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 film

Claims (5)

A protective film-forming film having energy ray curing properties; the protective film-forming film has a near-infrared transmittance of 1300 nm or less; the protective film-forming film is temperature-controlled at 30°C for 1 minute, and then the enthalpy (△H1) of the film after irradiation with ultraviolet rays for 1 minute is measured by differential scanning calorimetry (DSC) under the conditions of an illumination of 140 mW/ ^cm2 and a light quantity of 8120 mJ/ ^cm2 , and the enthalpy (△H2) of the film after irradiation with ultraviolet rays for 1 minute is measured again under the same conditions after temperature-controlled at 30°C for 1 minute, and the enthalpy (△H) obtained by the following formula (1) is not less than -100 J/g and less than 0 J/g; △H=△H1-△H2 ···(1). 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 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 described in claim 1 or 2. A kit comprising: a first laminated body in which a first peeling film and a protective film-forming film are laminated in order; and a support for supporting a workpiece to which the protective film-forming film is attached and the protective film-forming film. piece; The aforementioned 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.

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